TWI258635B - Undercoating material for wiring, embedded material, and wiring formation method - Google Patents

Abstract

This invention provides an undercoating layer material and a filler material containing a resin component having at least a substituent group which is capable of releasing a terminal group to form a sulfonic acid residue upon application of predetermined energy, and a solvent. The resin component has at least a repeating unit represented by formula (1), wherein n is an integer of 1 or more, X represents a C1 to C10 linear or branched alkyl chain, an aromatic or alicyclic alkyl chain or an alkyl ester chain, and Y is a substituent group forming a sulfonic acid residue upon application of predetermined energy.

Description

1258635 (1) Rose, invention description [Technical field to which the invention belongs]

The present invention relates to an underlayer film forming material, an embedding material, and a circuit forming method using the same for forming a circuit on a semiconductor substrate. In the lower layer film, (a) the photoresist layer is formed on the substrate before forming the photoresist layer. When the photoresist pattern is formed, the reflected light from the substrate surface can be prevented from entering the photoresist, and the pattern is improved. The lower layer film of resolution, (b) is characterized in that: the photoresist layer for lithography used to form the circuit is composed of a film formed by an organic film and a layer of a photoresist layer containing a top layer of germanium to improve the photoresist The pattern-accuracy of the second layer of photoresist is suitable for the underlayer film, and (c) is characterized in that the photoresist layer for lithography used to form the circuit has at least an underlayer film, an interlayer film and light formed by the organic film. A suitable underlayer film of a multilayer photoresist process that resists the multilayer structure of the upper film to improve the pattern accuracy of the photoresist. The embedding material is configured to form a first etching space formed by at least a low dielectric layer formed on the substrate, and a second etching space that communicates with the first etching space and is different in shape and size from the first etching space. Double Damascus structured etching space embedding material. [Prior Art] As is well known, a semiconductor substrate is formed by laminating a dielectric layer (insulator layer) on a substrate such as a germanium wafer, and patterned by a conductor layer in the dielectric layer of the semiconductor substrate (circuit The formation of the layer constitutes a semiconductor circuit structure. The formation of the above circuit layer has the use of a method that is quite different. The first side-5 - (2) 1258635 method, uniformly forming a conductor layer on the dielectric layer, forming a photoresist on the conductor layer, and irradiating (exposing) the photoresist by pattern light to form a photoresist In the pattern, the photoresist pattern is used as a mask, and the conductor layer is patterned into a circuit layer by etching, and after removing the photoresist pattern, a dielectric layer is further laminated to form a circuit in the dielectric layer. Floor.

In a second method, a photoresist pattern is formed on the dielectric layer, and the photoresist pattern is used as a mask, and a circuit trench is formed in the dielectric layer by etching to remove the photoresist pattern. The conductor material is embedded in the circuit trench, and the dielectric layer is laminated thereon to form a semiconductor circuit structure. In the multilayering of the circuit structure, the circuit layer forming process of each of the above methods is repeated, and a plurality of circuit layers are laminated, and a circuit formation process is required between the circuit layer forming processes. The via circuit forming process is formed by forming a via hole as a dielectric layer of an interlayer insulating layer between the lower circuit layer and the upper circuit layer, and depositing the conductor material or embedding the conductor material in a vapor phase manner in the via hole. To form a process of electrically connecting the lower circuit layer and the via circuit of the upper circuit layer.

In any of the above two circuit forming methods, when the photoresist layer is exposed and patterned, the exposure light is transmitted through the photoresist layer, and the transmitted light is reflected on the surface of the lower layer to generate an unexposed portion in which the reflected light is incident on the photoresist layer. The phenomenon of share. As the reflected light enters the photoresist layer, the pattern resolution of the photoresist deteriorates. Therefore, before the photoresist layer is formed on the semiconductor substrate, a resin composition containing a material having the property of absorbing exposure light is applied onto the substrate to form an underlayer film, and a method of forming a photoresist layer on the underlayer film is employed. . Focusing on this target action of the underlying film, it is also referred to as an anti-reflection film. There are various proposals for the material of the antireflection film. For example, there is a proposal for a resin composition containing an isocyanate group and a solvent as described in JP-A-6-319601. Further, as disclosed in JP-A-2-200- 5 1 2 3 3, there is development of a light-absorbing polymer containing a polymer having a hydroxystyrene monoethyl group having a sulfonate. Specific substituents for the acid ester. As disclosed in Japanese Laid-Open Patent Publication No. 2000-512402, there is a proposal for forming an antireflection film forming material comprising the above light absorbing polymer and a solvent. The underlayer film having the reflection preventing characteristic of the exposure light must have a photoresist pattern as a mask in addition to the reflection preventing property of the main purpose, and the etching process of the lower conductor layer or the dielectric layer may be completed by means of the method. Remove the characteristics. In the above-mentioned conventional underlayer film, the anti-reflection film material disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. The base polymer is insoluble in the stripping solution for photoresist. Therefore, in the technique disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 10-19601, after the upper photoresist pattern is removed by the stripping liquid, the remaining underlayer film is removed by plasma polishing. The resin component disclosed in the above-mentioned JP-A-2000-512336 and JP-A-2000-51 2402 is also insoluble in the resist stripping solution, and after removing the photoresist pattern by the stripping solution, it is still polished by the 电2 plasma. The residual underlayer film is removed. As is well known, in the construction of a semiconductor circuit, the dielectric layer covering the circuit layer and the other circuit layer resistive layer should have a low permittivity as much as possible without affecting the electrical characteristics of the circuit layer. When the permittivity of the dielectric body is low, specifically, the permittivity k is 3.0 or less. Such a low-permittivity material has low resistance to 02 plasma grinding, and is easily deteriorated upon exposure to the 〇2 plasma's surface, and has an increased capacity of -7-(4) 1258635. The above-mentioned conventional anti-reflection film is formed on a semiconductor substrate using such a low dielectric layer, and when the circuit layer is formed, the dielectric layer is etched by the plasma for removing the anti-reflection film, and the permittivity is increased. The deterioration is large, and as a result, there is a problem that the electrical characteristics of the circuit layer are adversely affected. In the manufacture of a semiconductor circuit structure, as described above, a circuit layer is formed by etching on a semiconductor to form a circuit trench for embedding a circuit layer, and a pattern of a photoresist and a lower film is formed by lithography. The control factors of the lithography process include the current 値 of the stepper for generating exposure light, the control of the voltage 値, the adjustment of the focal length of the lens, the accuracy of the reticle, the accuracy of the mounting position, and the coating characteristics of the photoresist composition, and hardening. There are many factors such as characteristics. If these control factors change for some reason, the patterning will occur and the lithography process must be corrected. At this time, when the semiconductor substrate is discarded and a new semiconductor substrate is used, resources are wasted and the environment is adversely affected. Therefore, in the related process, the imperfect photoresist layer and the underlying film are removed by lithography, and the semiconductor substrate is recovered. In the process of regenerating and recovering such a semiconductor substrate, the removal process of the underlayer film is referred to as a rework process, and an important process is considered in consideration of the economics of the manufacture of the semiconductor circuit structure. When the above-mentioned conventional antireflection film is examined from the viewpoint of such rework processing, a conventional antireflection film is not required, and it is not preferable to remove the non-used 02 plasma, and the characteristics of the semiconductor substrate after the reprocessing are not deteriorated. On the other hand, in the above-described apparatus having a circuit structure, high integration has been a frequent problem, and there is a demand for further miniaturization of circuits. The miniaturization of the circuit must improve the pattern resolution of the photoresist for lithography and enhance the pattern resolution of the etched circuit layer or circuit trench using the exposed photoresist pattern as a mask. Photoresist layer -8- (5) The thinner the film thickness of 1258635, the better the accuracy of using the exposure device and the circuit pattern mask on the photoresist transfer pattern. On the other hand, if the film thickness of the photoresist layer is thin, it is difficult to maintain the photoresist resistance of the photoresist layer during the etching process of the lower layer with the photoresist pattern as a mask, and it is easy to etch the circuit layer or circuit trench. The resolution has an adverse effect. In order to improve the resistance to light resistance, the film thickness is preferably thick. Thus, in order to improve the precision of the lithography using the photoresist, the setting of the thickness of the photoresist film has a contrary requirement. The technique for improving the lithography accuracy of the use of the photoresist is provided by a circuit forming method using a two-layer photoresist including a germanium, and a circuit forming method using a multilayer photoresist (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. In the circuit forming method of the former, the photoresist is not a single layer, but is a two-layer structure, and the photoresist film is thickened while the pattern transfer precision is improved. The technique is firstly to form a thick film underlayer film formed of an organic polymer material on a substrate, and a photoresist upper film formed of a film containing a ruthenium-containing photoresist having high resistance to oxygen plasma etching is formed thereon. Then, the transfer circuit pattern is formed on the photoresist upper film to form an upper photoresist pattern. Next, the resulting upper photoresist pattern is used as a mask, and the photoresist underlayer film is patterned by oxygen plasma etching. As a result, a photoresist film having a large thickness and a high pattern transfer precision can be obtained. The constituent material of the above-mentioned two-layered photoresist containing ruthenium is disclosed, for example, in JP-A-2002-033257. In Japanese Laid-Open Patent Publication No. 2002-033257, the underlayer film is referred to as a first photoresist layer, and the upper photoresist layer is referred to as a second photoresist layer. The constituent material of the first photoresist layer is generally a condensed polymer compound such as enamel resin, phenol resin or cresol resin, and an aromatic ring such as a phenyl group or a condensed aromatic ring such as a naphthyl group or a fluorenyl group in the side chain. Base polymers are also suitable for use in a variety of conventional photoresists. -9- (6) 1258635 Further, a ruthenium-containing photosensitive composition for the above second photoresist layer can be represented by a known one. The above-mentioned germanium-containing two-layer photoresist process is masked by its photoresist pattern, and after the etching process of the lower conductor layer or the dielectric layer is completed, it must be removed by some means. In Japanese Laid-Open Patent Publication No. 2002- 03 3 25 No. 7, a photoresist film having a top layer containing ruthenium is removed by a wet stripping treatment peculiar to the patent, and the remaining underlayer film is removed by grinding with 02 plasma. As is well known, in semiconductor circuit construction, the dielectric layer covering the circuit layer electrically isolated from other circuit layers is not affected by the electrical characteristics of the circuit layer, and may have a low permittivity. When the permittivity of the dielectric body is low, specifically, the permittivity k is 3.0 or less. Such a low permittivity material has low resistance to 〇2 plasma grinding. After exposure to 〇2 plasma, the surface is easily deteriorated and the permittivity is also increased. In the semiconductor substrate using such a low dielectric layer, the photoresist pattern formed by the above-mentioned conventional germanium-containing two-layer photoresist is formed, and when the circuit layer is formed, the 〇2 plasma polishing medium for removing the underlying film on the substrate is formed. The electric layer is eroded, and the deterioration of the permittivity is likely to occur, and as a result, there is a problem that the electrical characteristics of the circuit layer are adversely affected. Further, in the manufacture of the semiconductor circuit structure, as described above, the circuit layer is formed by etching on the semiconductor, and the circuit trench for embedding the circuit layer is formed, and the photoresist is patterned by lithography of the underlying film. The control factor of the lithography process is the current 値 of the stepper for generating exposure light, the control of the voltage 値, the adjustment of the focal length of the lens, the thickness of the photoresist, the mounting position accuracy, and the coating characteristics of the photoresist composition. Many factors such as hardening characteristics exist. These control factors -10 - (7) 1258635 change for some reason, and the patterning is poor, resulting in the need to correct the lithography process. At this time, when the semiconductor substrate is discarded and a new semiconductor substrate is used, resources are wasted and the environment is adversely affected. Therefore, in the related process, the lithographic photoresist layer and the underlying film are removed, and the semiconductor substrate is recovered. The underlayer film removal process for the process of regenerating and recovering such a semiconductor substrate is referred to as a rework process, and in consideration of the economics of the manufacture of the semiconductor circuit structure, it is an important process, and the above-mentioned lower layer is discussed from the viewpoint of such rework processing. In the case of the film, it is not known that the removal of the underlayer film is not performed by the 〇2 plasma, and the problem that the characteristics of the semiconductor substrate are easily deteriorated after the rework treatment is not appropriate. The technique in which the photoresist layer is substantially a two-layer structure is different from the technique using the above-described ytterbium-containing two-layer photoresist, and a technique for preventing reflection of exposure light and providing an underlayer film under the photoresist layer is known. The underlayer film is composed of a resin composition having high absorption characteristics of exposure light, and absorbs the patterned light of the upper photoresist to prevent it from reaching the substrate surface, thereby achieving the effect of not generating reflected light of the exposure light. The material forming the underlayer film should also be transferred to form the above-mentioned underlayer film containing the second layer of photoresist. If the reflection preventing film can be removed without using 〇2 plasma polishing, the problem of the above-described circuit forming method including the bismuth two-layer photoresist can be solved. The material of the above-mentioned antireflection film has been proposed as various materials. For example, there is a proposal of a resin composition containing a polymer having an iminosulfonic acid group and a solvent (Japanese Laid-Open Patent Publication No. Hei No. Hei 10-319601). And development of a light-absorbing polymer containing a polymer having a hydroxystyrene unit, the unit having a specific substituent containing a sulfonic acid ester (Japanese Patent Publication No. 2000-511 2336) containing the light-absorbing polymer And proposals for the anti-reflection film forming material of the solvent (Japanese Patent Publication No. 2000-5124-2). The anti-reflection film material disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. 3-19601, wherein the resin component is a polymer having an imidosulfonic acid group, and the resin component is insoluble in the peeling of the photoresist. liquid. Therefore, the technique disclosed in Japanese Laid-Open Patent Publication No. Hei 10-3-19601, after removing the photoresist pattern of the upper layer by the stripping solution, removes the remaining underlayer film by 〇2 plasma polishing. Further, the resin components disclosed in the above-mentioned Japanese Patent Publication No. 2000-512336 and No. 2000-512402 are not dissolved by the resist stripping solution, and the stripping liquid must be removed by the 〇2 plasma after removing the photoresist pattern. Sanding removes residual underlayer film. Therefore, the transfer of the conventional anti-reflection film to the underlayer film containing the bismuth layer of the photoresist is still unresolved with the removal of the underlying film. The latter method of forming a circuit of the latter (i.e., Japanese Laid-Open Patent Publication No. Hei 10-92740), that is, a multilayer photoresist process, in which the photoresist is not a single layer, and has a multilayer structure, (1) initially converting the pattern from the reticle The uppermost photoresist film is printed, and the decomposition energy and depth of focus in lithography are improved. (2) Under the uppermost film, a multi-layered film has a small interference effect, and an anti-uranium anti-reflection film is high. It can obtain the technology of high transfer precision and dry uranium engraving resistance and excellent resistance pattern. This technique first forms a composite anti-reflection film on a substrate. The composite antireflection film is made of, for example, a carbon film and a tantalum oxide film, and if necessary, a multilayer film of a tantalum nitride barrier layer is provided between these. A thin film upper photoresist film is formed on the multilayer film. Then, the circuit pattern is transferred to the photoresist upper film by lithography to form an upper photoresist pattern. Next, using the obtained upper photoresist pattern as a mask, the intermediate layer tantalum oxide film was etched and the pattern was transferred. Then, the underlying photoresist pattern and the intermediate layer pattern are used as masks, and the underlying film carbon film is etched to transfer the circuit pattern. Finally, the above-mentioned upper photoresist pattern and the intermediate layer - 12 - 1258635 Ο) are removed, and the carbon film (lower film) pattern with good dry etching resistance and high pattern transfer precision is obtained. The underlying film pattern carbon film pattern is used as a mask, and the substrate is etched according to the pattern. In the above-mentioned multilayer photoresist, the pattern of the underlying film (carbon film) remaining at the end, and the patterning of the etching process of the lower conductor layer or the dielectric layer is completed by some means. JP-A-11-92740 is removed by grinding with 〇2 plasma. As is well known, in a semiconductor circuit structure, a dielectric layer covering the circuit layer as an electrically isolated dielectric layer does not affect the electrical characteristics of the circuit layer, and the stomach must have a low permittivity as much as possible. The dielectric material has a low permittivity, and specifically, the capacitance k must be 3.0 or less. Such a low permittivity material has low resistance to 〇2 plasma polishing, and is exposed to 〇2 plasma, and the surface is easily deteriorated, and the permittivity is also increased.

In the semiconductor substrate using such a low dielectric conductor layer, the photoresist pattern formed by the above-mentioned conventional multilayer photoresist is formed, and when the circuit layer is formed, the dielectric is polished by the 〇2 plasma for removing the underlying film on the substrate. The body layer is eroded and is prone to the deterioration of its permittivity, resulting in a problem that adversely affects the electrical characteristics of the circuit layer. Further, in the manufacture of the semiconductor circuit structure, as described above, a circuit layer is formed on the semiconductor by etching, and a circuit trench for embedding the circuit layer is formed, and patterning is performed by lithography of the photoresist or the underlying film. The control factors of the lithography process are: current 値, voltage 値 control of the stepper for generating exposure light, adjustment of the focal length of the lens, accuracy of the reticle, accuracy of mounting position, and coating characteristics of the photoresist composition, There are many factors such as hardening characteristics. These control factors are changed by -13 - (10) 1258635 for some reason, and the patterning is poor, which makes the non-adjusting lithography process impossible. In this case, the disposal of the semiconductor substrate and the use of a new semiconductor substrate are wasteful of resources and adversely affect the environment. Therefore, in the related process, when it is known that the lithography is defective, the photoresist remaining on the substrate must be removed to recover the semiconductor substrate. Such a process of removing the defective photoresist during the process of recycling and recovering the semiconductor substrate is called a rework process, and is an important process in consideration of the economics of the manufacture of the semiconductor circuit structure. When the above-mentioned conventional underlayer film is examined from the viewpoint of such rework processing, the conventional underlayer film is not removed by the use of the non-ruthenium 2 plasma, and the problem that the characteristics of the semiconductor substrate after the rework treatment are easily deteriorated is not appropriate. Further, the so-called poisoning phenomenon which occurs frequently when a low dielectric layer is used for supporting the interlayer insulating layer of the above-mentioned circuit layer has recently become a problem in the formation of a photoresist pattern and needs to be solved. The above poisoning phenomenon is apt to occur when a low dielectric layer is used in the interlayer insulating layer, and the above-mentioned underlying material cannot be prevented from occurring. Therefore, in the circuit formation process using a low dielectric layer, it is still expected to be easy to remove after use and to suppress the development of a film material under poisoning. While the photoresist layer is a technique of a substantially layer (two-layer) structure, a technique different from the technique of using a multilayer photoresist, in order to prevent reflection of exposure light, a technique of providing an underlayer film under the photoresist layer is known. This underlayer film is composed of a resin composition having high absorption characteristics of exposure light, and absorbs the patterned light of the upper layer resist to prevent it from reaching the substrate surface, and functions to prevent the reflected light of the exposure light from being generated. If the anti-reflection film can be removed without grinding with 〇2 plasma, and the adverse effect on the photoresist film caused by poisoning can be suppressed, the problem of the circuit formation method using the above multilayer photoresist can be -14 - (11) 1258635 solve. The above-mentioned antireflection film material has been proposed as a variety of materials. There is a proposal of a resin composition containing, for example, a polymer having an iminosulfonic acid group and a solvent (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. And development of a light-absorbing polymer containing a polymer having a hydroxystyrene unit having a specific substituent containing a sulfonate group (Japanese Patent Publication No. 2000-511 2336) containing the light absorbing polymerization Proposal for anti-reflection film forming materials of materials and solvents (Japanese Patent Publication No. 2-512402). The anti-reflection film material disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Therefore, the technique disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. The resin component disclosed in the above-mentioned publication No. 2000-51 23 36 and the special publication No. 20 00 - 5 12402 is also insoluble in the photoresist stripping solution, and must be removed after removing the photoresist pattern with the stripping solution. 2 plasma grinding to remove residual underlayer film. Therefore, the use of the conventional antireflection film as the underlayer film does not solve the problem of removal with the underlayer film. However, if attention is paid to the basic circuit configuration of the semiconductor integrated circuit, the basic circuit configuration is, as is well known, formed directly or indirectly on the lower circuit layer on the semiconductor substrate, and the lower circuit layer is formed by interlaminar insulating film. The upper circuit layer has a structure in which a via circuit formed by penetrating the interlayer insulating film is connected. This circuit structure is multi-layered and multilayered to form a multilayer circuit structure of a semiconductor body circuit. - 15 - (12) 1258635 A method for realizing such a multilayer circuit using copper with excellent electromigration resistance is known as a dual damascene process. The dual damascene process system forms a first etching space formed by at least a low dielectric layer formed on a substrate, and a second etching space which is in communication with the first etching space and has a shape and size different from the first etching space. Double damascene structure. The embedding conductor material is constructed in the double damascene structure to realize the above circuit configuration. The basic process of the dual damascene process is illustrated with reference to Figures 1A through 1D and Figures 2E through 2H. First, as shown in FIG. 1A, an interlayer insulating film 2 is formed on the substrate 1. The material constituting the interlayer insulating film 2 is SiO 2 , carbon doped oxide (SiON ), SOG (spin on glass) or the like. A photoresist film 3 is formed on the interlayer insulating film 2, and is patterned. The patterned photoresist film 3 is used as a mask for selective etching of the interlayer insulating film 2, followed by removal of the photoresist layer 3, as shown in Fig. 1B, to form a trench 4 . Next, on the surface of the interlayer insulating film 2 on which the circuit trench 4 is formed as described above, a barrier metal 5 is deposited on the inner surface of the circuit trench 4 to form adhesion for enhancing the adhesion of the copper and the interlayer insulating film 2 embedded in the circuit trench 4. At the same time, the barrier metal film which diffuses copper into the interlayer insulating film 2 is prevented. Then, as shown in Fig. 2C, copper is buried in the circuit trench 4 by electroplating or the like to form the lower circuit layer 6. Next, the copper adhered to the surface of the interlayer insulating film 2 at this time and the residual barrier metal 5 are removed by chemical honing (CMP), and the surface of the interlayer insulating layer 2 is planarized, and then laminated thereon in order. The low dielectric layer 7, the first etch stop film 8, the second low dielectric layer 9, and the second etch stop film 10. Next, on the second etch stop film 10, a photoresist mask 11 having a pattern for forming via holes is formed. Next, as shown in FIG. 1D, etching is performed by the photoresist mask - 16 - (13) 1258635, forming a second etch stop film 1 Ο, a second low dielectric layer 9, a first etch stop film 8 and A low dielectric layer 7 reaches the via 12 of the surface of the underlying circuit layer 6. Then, as shown in Fig. 2, the embedding material 13 such as the photoresist layer 3 is filled in the via hole 12. The embedding material 13 is etched, as shown in Fig. 2F, leaving only a specific thickness at the bottom of the via hole 12, and a photoresist mask 14 having a pattern for trench formation is formed on the second etch stop film 10. With the photoresist mask 14, as shown in Fig. 2G, the second etch stop film 1A and the second low dielectric layer 9 are etched to form the trenches 15, while the embedding material 13 remaining at the bottom of the via holes 12 is removed. Then, copper is buried in the via hole 12 and the trench 15, and as shown in Fig. 2H, the via circuit 16 and the upper circuit layer 17 are formed. Thereby, the multilayer circuit structure 6 and the upper circuit layer 17 are electrically connected to each other by the multilayer circuit structure. In the multilayer circuit structure obtained by the above process, the trench corresponds to the first etching space or the second etching space, and the via hole corresponds to the second etching space or the first etching space. Therefore, in the above-described process of Fig. 1, the trench 15 and the via hole 12 under the trench 15 constitute a double damascene structure. In the above method for forming a double damascene structure, there is a use of an embedding material, and the function of the embedding material is as follows. That is, after the via hole is formed, the underlying substrate of the via hole is exposed by etching, and the underlying circuit layer exists on the surface of the substrate, which is damaged by the etching gas for forming the trench, which may cause a circuit failure or the like. Therefore, the embedding material is filled in the via hole to protect the underlying circuit layer during the trench formation process. The embedding material is always a photoresist composition, and when the photoresist composition is filled in the via hole, bubbles are generated and the embedding is insufficient. Therefore, a solution in which a thermally crosslinkable compound is dissolved in an organic solvent is used. Proposal for new embedding materials (JP-2002- -17 - (14) 1258635 03 3257). However, in the structure in which the organic film is used as an embedding material, the removal of the embedding material remaining in the interlaminar pores after the action of the embedding material is not easy, and it is necessary to perform the removal treatment by oxygen plasma polishing. At this time, the polishing gas (mainly an oxygen-based gas) is damaged by the low dielectric layer. The damage is such that the Si-R of the low dielectric layer becomes Si- Η Η, or the permittivity (k) is increased. When a circuit layer is formed, a photoresist is used, and the patterning is performed by exposure, but it is known that if the exposure light is reflected by the surface of the underlying layer of the photoresist, the reflected light is incident on the non-exposed portion of the photoresist, and the pattern is formed. The problem of poor resolution. In order to prevent this anti-reflection, a technique of providing an underlayer film under the photoresist layer is known, and the underlayer film is composed of a resin composition having high absorption characteristics of exposure light, and absorbs pattern light of the upper layer photoresist to avoid arrival. The surface of the lower layer of the photoresist is such that the exposure light does not produce reflected light. The material forming the underlying anti-reflection film should also be transferred to the embedding material for forming the above dual damascene structure. If the anti-reflection film can be removed without grinding with 〇2, the problem in the method of forming the double damascene structure described above can be solved. The material of the above-mentioned antireflection film has been proposed as various materials. For example, there is a proposal of a resin composition containing a polymer having an iminosulfonic acid group and a solvent (JP-A-10-319601). There is also the development of a light-absorbing polymer containing a polymer having a hydroxystyrene unit, which unit has a specific sulfonate-containing group (Japanese Patent Publication No. 2000-5512), which contains the light absorbing polymer. Proposal for the anti-reflection film forming material of the object (Japanese Patent Publication No. 2000-512402). The anti-reflection film material disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. . Therefore, in the technique disclosed in Japanese Laid-Open Patent Publication No. Hei 10-319601, after the upper photoresist pattern is removed by the stripping liquid, the residual underlayer film is removed by 02 plasma polishing. Further, the resin component disclosed in the above-mentioned Japanese Patent Publication No. 2000-512336 and Japanese Patent Publication No. 2000-512402 is also insoluble in the resist stripping liquid, and the resist pattern is a stripping liquid removing liquid, and the residual underlayer film must still be 〇 2 plasma grinding to remove. Therefore, the conventional use of the antireflection film for the use of the % embedding material for the formation of the double damascene structure still does not solve the problem of the removal of the embedding material. ^ In this regard, it is considered to use a spin-on glass material as an embedding material for the formation of a double damascene structure. A spin-on glass material is used for the embedding material, as disclosed in, for example, U.S. Patent No. 63 29 1 1 8 . The spin-on glass material can be removed by the stripping solution, and the residual embedded material can be removed without using the 〇2 plasma to avoid the problem of degradation of the low dielectric layer.

However, the so-called poisoning phenomenon occurs frequently when the low dielectric layer is used to support the interlayer insulating layer of the circuit layer, which has recently become a problem in the formation of the double damascene structure, which is embedded in the use of the above-mentioned spin-on glass material. In the case of materials, the same problems have occurred in the use of the 包2 plasma-cleaning type of embedding material, which still needs to be solved. In the above poisoning, the shape of the second etching space 15 which is obtained during the circuit forming process of Fig. 2G causes a serious flaw. Fig. 3 is a schematic diagram showing the etching space in a normal and spatial shape. The third A picture shows no poisoning phenomenon, the enlarged top view of the important part when the groove (second etching space) 15 can be formed normally, and the poisoning phenomenon occurs in the third B picture (the second saturated space -19- (16) 1258635 ) An enlarged plan view of important parts when the shape of the 1 5 is poor. In the third embodiment, the same components as those of the first and second figures are denoted by the same reference numerals and the description will be simplified. Moreover, the magnification of FIG. 3B is larger than that of FIG. 3A. It can be seen from the figure that when the poisoning phenomenon occurs, the embedding material and the photoresist layer are deteriorated due to the alkaline substance generated from the low dielectric layer 9, so that the photoresist pattern is coated on the via hole (first hungry space) 12, The shape of the groove 15 is disorderly. The above poisoning phenomenon is apt to occur when a low dielectric layer is used for the interlayer insulating layer. The conventional embedding material for forming a double damascene structure cannot be prevented from occurring. Therefore, in the double damascene structure forming process using a low dielectric layer, the characteristics of being trapped in the etching space, the ease of removal after use, and the embedding material capable of suppressing poisoning phenomenon are currently to be developed. [Summary of the Invention]

The present invention has been made in view of the above problems, and a first object thereof is to provide high light absorption of an exposure light, excellent resistance to a 2.38 wt% TMAH developing solution generally used for a photoresist development process, and peeling off by a photoresist after use. The liquid film is removed, and the sub-membrane material which is easy to be processed by the substrate is easily processed. A second object of the present invention is to provide an underlayer film material for a ruthenium-containing two-layer photoresist process which is excellent in resistance to a photoresist developing solution and which can be removed by a photoresist stripping solution after use. The third object of the present invention provides an excellent resistance to a photoresist developing solution, good patterning property, resistance to an alkaline compound, and suppression of a defect caused by poisoning in a resist pattern. The effect is more than the use of the photoresist stripping solution after use, and the multilayer reprocessing of the substrate is easy to process. The fourth layer of the present invention is provided to maintain the embedding into the etching space. The embedding material for forming a double damascene structure which can be easily removed after use and which can suppress poisoning. Further, the present invention provides a method of forming a circuit using the above-mentioned underlying material and embedding material. In order to solve the above problems, the inventors of the present invention have repeatedly and experimentally discovered that it is possible to form a lower layer film material by using a resin containing at least a substituent having a specific energy end group derived from a sulfonic acid residue to be removed as a resin component. ^ Good effect and effect. In addition, the present inventors have found that a resin containing at least a substituent having a specific energy and a terminal group derived from a sulfonic acid residue can be used as a resin component to constitute an embedding material, thereby maintaining the embedding property in the etching space and using the resin. After the removal is easy to produce, while inhibiting poisoning.

That is, the underlayer film formed using the underlayer film material as described above has high resistance to the 2.38 wt% TMAH developing solution for developing the exposed photoresist layer, and is formed under application of a specific energy. The terminal group of the resin component of the underlayer film is partially sulfonated, and becomes compatible with the water-soluble amine and the quaternary oxide. These solutions containing a water-soluble amine and a quaternary ammonium hydroxide can be used for the photoresist stripping solution, and the underlayer film can be peeled off by a photoresist stripping treatment and a stripping treatment by a photoresist containing an upper layer of germanium. When a lower layer film is formed by applying a specific energy as described above, the terminal group of the component resin forming the underlayer film has been sulfonated, the sulfonic acid group becomes a terminal group, and the lower layer film is a water-soluble amine, four Ammonium hydroxide - 21 - (18) 1258635 is compatible. These solutions containing a water-soluble amine and a quaternary ammonium hydroxide can be easily peeled off by a photoresist stripping solution because of a stripping solution which can be used for photoresist, and do not invade the low dielectric layer. Therefore, the underlayer film can suppress the deterioration of the pattern of the photoresist pattern caused by the poisoning phenomenon. Thus, the inventors of the present invention have found that an underlayer film is formed by a "lower film material containing a resin having at least a specific energy and a terminal group is desorbed from a substituent which generates a sulfonic acid residue as a resin component", and is formed in a photoresist process. Because the commonly used 2.38 wt% TMAH imaging solution has high resistance, the photoresist does not deteriorate during development, and can be easily removed by the photoresist stripping solution, not only the process can be simplified, but also the substrate is not removed. Deterioration of the dielectric layer. That is, the underlayer film forming material for lithography processing (hereinafter referred to as the first underlayer film forming material of the present invention) is formed by forming a photoresist for forming a circuit pattern on a semiconductor substrate. The material of the underlayer film on the substrate is characterized in that it contains a resin component and a solvent having at least a specific energy and a terminal group is desorbed from a substituent which generates a sulfonic acid residue. A circuit forming method using the underlayer film forming material (the first circuit forming method of the present invention) is characterized in that, on the substrate, a material is formed by using the underlayer film of the above lithography to form a film under the underlayer film. a process of forming a photoresist layer on the underlying film, applying an exposure and development process to the photoresist layer to form a photoresist pattern forming process of a specific photoresist pattern, and not forming the lower layer covered by the photoresist pattern The exposed portion of the film is removed by dry etching to remove the underlying film patterning process. The photoresist pattern and the patterned underlayer film are used as masks, the circuit pattern forming process for etching the substrate to form a specific circuit pattern, and the formation of the above circuit pattern are formed. The underlying film and the photoresist pattern remaining on the substrate are then removed by the light-22-(19) 1258635 resist stripping solution while removing the underlying film removal process. The following effects can be obtained by the features of the first underlayer film forming material and the first circuit forming method. (1) The material for forming a layer film of the present invention is insoluble in a photoresist developing solution. Therefore, it is not problematic to remove the side wall side etching and the undercutting dimensional control which are unavoidable by removing the underlying film by the developing liquid. (2) Because the photoresist stripping solution can be removed, it is suitable for laminating a semiconductor substrate of a low-dielectric material such as a low dielectric material having a permittivity (k) of 3.0 or less. Use the underlying film material. (3) When it is necessary to regenerate the substrate due to lithography, the processing of the underlayer film and the substrate regeneration can be easily and easily performed by wet processing with less damage to the substrate. Further, the underlayer film forming material for the two-layer photoresist process according to the present invention (hereinafter referred to as the second underlayer film forming material of the present invention) constitutes a bismuth-containing light for forming a circuit layer with high precision on a substrate. The material for forming the underlayer film is characterized in that it contains a resin component and a solvent having at least a specific energy and a terminal group is desorbed from a substituent which generates a sulfonic acid residue. A circuit forming method using the underlayer film forming material (hereinafter, the second circuit forming method of the present invention) is characterized in that it is included on a substrate, and the underlayer film forming material for the ytterbium-containing two-layer photoresist process is used to form a photoresist Underneath the underlayer film formation process, a photoresist upper layer film is formed on the underlying film by using a ruthenium-containing photoresist material, and the photoresist upper layer film is subjected to exposure and development processing to form a photoresist pattern on the upper surface of the specific photoresist pattern. Forming process, the exposed portion of the underlying film not covered by the upper photoresist pattern is formed by dry etching to remove the underlying photoresist pattern to form a -23-(20) 1258635 process' with the upper photoresist pattern and the lower photoresist The pattern is a mask, the circuit pattern forming process for etching the substrate to form a specific circuit pattern, and the lower photoresist pattern and the upper photoresist pattern remaining on the substrate after the circuit pattern is formed are simultaneously removed by the photoresist stripping liquid. Photoresist pattern removal process. The following effects can be obtained by the features of the second underlayer film forming material and the second circuit forming method. (1) The underlying film of the present invention is removed by a photoresist stripping solution, and is suitable for use as a low dielectric material such as a permittivity (k) of 3.0 or less. 打2 is used to polish plasma resistance and low dielectric laminated semiconductors. The underlying material of the lithography process of the substrate. (2) When it is necessary to regenerate the substrate due to lithography, the underlayer film can be easily removed by wet processing with less damage to the substrate, and the reprocessing of the substrate can be reliably and easily performed. As a result, it is difficult to dissolve the yttrium-containing photoresist which is generated by polishing with 〇2 plasma, and it is difficult to dissolve the underlying film, which makes it difficult to regenerate the substrate. As described above, the inventors of the present invention have found that the underlayer film for a multilayer photoresist formed of a resin component containing at least a specific energy and a terminal group which is free from the terminal to generate a sulfonic acid residue is used as a resin component underlayer film material. Because of the high resistance of 2·38 wt% TMA Η imaging solution which is usually used in the photoresist development process, the upper photoresist film does not deteriorate during development, and is easily removed by the photoresist stripping solution. Not only can the process be simplified, but also the degradation of the substrate dielectric layer caused by the removal process. And learned that it can prevent the poor resistance of the photoresist pattern caused by poisoning. That is, the underlayer film forming material for the multilayer photoresist process according to the present invention (hereinafter referred to as the third underlayer film forming material of the present invention) is at least the lower layer for forming the final pattern of the circuit layer on the substrate. Membrane, interlayer film-24 - (21) 1258635 and the photoresist for lithography of the photoresist upper layer film are formed of the above-mentioned underlayer film forming material, which is characterized in that it contains at least a specific energy and the terminal group is detached to produce sulfonate. A resin component and a solvent of a substituent of an acid residue. A circuit forming method using the underlayer film (the third circuit forming method of the present invention) is characterized in that it is included on a substrate, and a material is formed by using the underlayer film for the multilayer photoresist process to form a film under the underlayer film. An intermediate layer film forming process for forming an intermediate layer film on the underlying film with a tantalum oxide film material forms a photoresist upper layer film on the intermediate layer film, and the photoresist upper layer film is subjected to exposure and development processing to form a specific a photoresist pattern forming process on the upper surface of the photoresist pattern, wherein the exposed portion of the intermediate layer film not covered by the upper photoresist pattern is formed by dry etching to remove the intermediate layer pattern, and the intermediate layer resist pattern is used as a mask The mask is subjected to dry etching to remove the underlying pattern forming process of the exposed portion of the underlying film which is not covered by the mask, and the circuit pattern forming process for forming a specific circuit pattern by etching the interlayer insulating layer on the substrate by using the underlying pattern as a mask And the above-mentioned lower layer pattern remaining on the substrate after the formation of the above circuit pattern is removed by a photoresist stripping solution. The following effects can be obtained by the features of the third underlayer film forming material and the third circuit forming method. (1) The underlying film of the present invention is removed by a photoresist stripping solution, and is suitable for laminating a semiconductor substrate of a material having low resistance to 〇2, such as a low dielectric material having a permittivity (k) of 3.0 or less. Film material under the lithography process. (2) When it is necessary to recover the substrate due to lithography, the underlayer film can be easily removed by wet processing with less damage to the substrate, and the reprocessing process for substrate recovery can be carried out reliably and easily. As a result, if the film containing -25-(22) 1258635 is polished by the 02 plasma, it is difficult to dissolve the yttrium-containing photoresist due to deterioration, and it is difficult to regenerate the substrate due to insolubilization of the underlying film. (3) Furthermore, if a multi-layer photoresist underlayer film and a double damascene process are used, the deterioration of the photoresist pattern is likely to occur due to the poisoning phenomenon caused by the formation of the double damascene structure in the low dielectric layer. Or inhibit. In order to solve the problem of the conventional embedding material, the inventors of the present invention have carefully and experimentally discovered that a resin containing at least a substituent having a specific energy and a terminal group desorbed to generate a 5-shell acid residue is formed as a resin component. By embedding the material, the embedding property to the etching space can be maintained, and the removal is easy after use, and the poisoning phenomenon is suppressed. That is, the underlayer film is formed using the embedding material as described above, and the resistance to the 2.38 wt% ΤΜΑΗ imaging liquid for the development of the exposed photoresist layer is high, and the underlayer film is formed when a specific energy is applied. A part of the terminal group of the resin component is sulfonated, and the water-soluble amine and the quaternary ammonium hydroxide become compatible. These solutions containing a water-soluble amine and a quaternary ammonium hydroxide are used as a stripping solution to peel off the embedded material in the first etching space after the second etching space is formed. As described above, the present inventors have found that an embedding material formed of "an embedding material containing a resin having at least a specific energy and a terminal group desorbing a substituent which generates a sulfonic acid residue as a resin component" is generally used for The resistance of the photo-resistance process is 2.38 wt%, the resistance of the developing solution is high, the photoresist is not deteriorated, and the photoresist stripping liquid can be easily removed. The process can be simplified, and the substrate is not removed by the removal process. The dielectric layer is deteriorated, and the pattern deterioration caused by the alkaline component of the low dielectric layer is suppressed, and the anti-poisoning property can be exhibited to a high degree. That is, the embedding material for forming a double damascene structure according to the present invention (the embedding material of the present invention under -26 - (23) 1258635) is used to form at least a low dielectric layer formed on the substrate. An etching space embedding material of the double damascene structure formed by the etching space and the second etching space which is different from the shape and size of the first etching space, and is characterized in that at least a specific energy is applied The terminal group is separated from the resin component and solvent which generate a substituent of the sulfonic acid residue. A method for forming a double damascene structure using the embedding material (the fourth circuit forming method of the present invention) is characterized in that: an interlayer insulating layer formed by laminating at least a low dielectric layer on a substrate having a metal layer In the interlayer insulating layer forming process, a photoresist layer is formed on the interlayer insulating layer, and after the pattern is exposed, a development process is performed to form a photoresist pattern, and the photoresist pattern is used as a mask for etching to form the interlayer insulating layer. a first etching space forming process of the first etching space, and coating the embedding material layer on the interlayer insulating layer by using the embedding material of the present invention, and embedding the embedding material in the first etching space Forming a photoresist layer on the embedding material layer, irradiating the photoresist layer with pattern light, and developing with an alkali developing solution to form a photoresist pattern type photoresist pattern forming process, and the photoresist pattern is formed by the photoresist pattern The mask is etched, and the interlayer insulating layer on the upper portion of the first etching space is removed according to a specific pattern to form a second etching space of the second uranium engraved space in communication with the first etching space. Cheng investment material, and the remaining space to the second etching is removed by the stripping liquid embedding material removal process. In the above configuration, the first uranium engraved space trench or via hole, and the second etched space refers to via hole or trench. According to the characteristics of the embedding material of the present invention and the fourth circuit forming method, -27 - (24) 1258635 can obtain the following effects. (1) The embedding material used in the present invention, because of the patterning process of the photoresist, the gaseous state of the low dielectric layer or the liquid alkali component is highly resistant, and the light generated by the above-mentioned components can be suppressed. The patterning type is poorly poisoned, and thus the patterning of the excellent dimensional stability of the etching space of the double damascene structure becomes possible. (2) Due to the removal of the available photoresist stripping solution, it can be applied as a semiconductor substrate for laminating a material of a low dielectric material such as a permittivity (k) of 3.0 or less. The etched space embedding material is used for the lithography process. Thus, the low permittivity of the low dielectric layer can be maintained after proper formation to form the circuit layer. The above matters, as well as other objects, features and advantages of the present invention, will become apparent from the Detailed Description of the invention. [Embodiment] The first underlayer film forming material (underlayer film forming material for lithography) of the present invention is characterized in that it contains a substituent having at least a specific energy and a terminal group is detached to generate a sulfonic acid residue. Resin component, and solvent. The second underlayer film forming material (the underlayer film forming material for a germanium two-layer photoresist process) of the present invention is characterized in that it contains a substituent having at least a characteristic energy applied and a terminal group is detached to generate a sulfonic acid residue. Resin composition, and solvent. The third underlayer film forming material (the underlayer germanium forming material for a multilayer photoresist process) of the present invention, as described above, is characterized in that it contains at least a specific -28-(25) 1258635 energy and the terminal group is detached to generate a sulfonic acid residue. The resin component of the substituent, and the solvent. The embedding material (embedded material for forming a damascene structure) of the present invention is characterized in that it contains a resin component having at least a specific energy and a terminal group is desorbed from a substituent which generates a sulfonic acid residue, and a solvent. In the above first, second and third underlayer film forming materials of the present invention, in the embedding material, the resin component is characterized by at least the following general formula (1)

(wherein n is an integer of 1 or more, X is a linear or branched alkyl chain having 1 to 10 carbon atoms, an aromatic or alicyclic cyclic alkyl chain, an alkyl ester chain, and the lanthanide is subjected to specific energy A repeating unit that applies a substituent that produces a sulfonic acid residue. The specific energy to be applied to the above-mentioned sulfonic acid residue may be, for example, a heat treatment at 80 ° C or higher to generate a sulfonic acid residue. The application of such specific energy can be further promoted by the combination of heating and alkali in the stripping treatment. The substituent Y of the above general formula (1) is preferably -S03R or -S03_R24 (wherein 1 and R2 are monovalent organic groups). The above-mentioned organic group Ri is preferably one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms or a hydroxy alkane-29-(26) 1258635 group. The above organic group R2 is preferably at least one selected from the group consisting of an alkanolamine and an alkylamine. The resin component which has at least a specific energy and the terminal group is desorbed from the substituent which generates a sulfonic acid residue may be a copolymer or mixed resin of any one of the above-mentioned resin components with a acrylic acid or methacrylic acid or such a derivative. . When the above-mentioned copolymer or mixed resin is used as the resin component, the polymerization ratio or the mixing ratio thereof is such that it can withstand the resistance of 2·38% by weight of TMA Η developing solution and can be removed by the photoresist stripping solution. There is no special restriction. The above resin component having at least a specific energy and a terminal group derived from a substituent which generates a sulfonic acid residue can be used. For the copolymer or mixed resin of any of the above resin components with acrylic acid or methacrylic acid or such derivatives, the following general formula (2)

(2) (wherein n is an integer of 1 or more, and r3 is selected from a hydrogen atom, a fluorine atom, a hydroxyl group 'carboxy group, a hydroxyalkyl group having 1 to 5 carbon atoms, and an alkyloxy group having 1 to 5 carbon atoms. At least one of the alkyl groups, a Z-based carbon atom to a straight chain or a branched alkyl chain of '1' or an alicyclic cyclic alkyl chain, an alkyl ester chain.) The copolymer component of the copolymer or the mixed resin of the resin compound having the repeating '30-(27) 1258635 unit of the above general formula (2) is a derivative copolymer of the above general formula (2), a polymer When the underlayer film material is composed of a resin component, the monolayer of the resin component is preferable because the lithography process using a KrF excimer laser is highly neutral. The solvent used for the underlayer film forming material of the present invention is not particularly limited as long as it is an underlayer film forming material, and can be used. Specifically, there are, for example, acetone, methyl ethyl ketone, cyclopentanone, cyclohexyl isopropyl ketone, 2-heptanone, ketone diol such as 1,1,^-trimethylacetone, ethylene glycol monomethyl ether, and B. Glycol monoethyl ether, ethylene glycol monobutyl glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ester, diethylene glycol, diethylene glycol monoacetate, diethyl Glycol monomethyl glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol, dipropylene glycol monomethyl ether, glycerin, 1,4-butanediol, 1,3 -, 2' 3-butanediol, etc. Polyols and their derivatives; such as dioxanes; ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl ester, ethyl pyruvate 'methyl 3-methoxypropionate, 3- Esters such as ethoxyethyl ester; sub-classes such as dimethyl ya mill; dimethyl mill, bis-hydroxy hydroxyethyl), and so on; N, N-dimethyl, N-A Indoleamines such as carbamide, N,N-dimethylacetamide, N-methyl, N,N-diethylacetamide; N-methyl-2-pyryl, N-ethyl- 2 pyrrolidone, n-hydroxymethyl-2-pyrrol each Intrinsic amines such as phenylethyl 2-pyrrolidone; - propiolactone butyrolactone, 7-valerolactone, δ-valerolactone, 7-caprolactone, ε Ketone, A; ether, ether acetate ether, dimethyl ether butanediol ring ether pyruvate propionic acid, bis (2 carbamide acetoxime oxime ketone, Ν X ry ——内-31 - (28) 1258635 Ester and other lactones; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl An imidazolidone or the like such as 2-imidazolidinone, etc. These may be used alone or in combination of two or more. The underlayer film forming material of the present invention may contain a crosslinking agent, and such a crosslinking agent may be used in the present invention. The resin component is crosslinked without any particular limitation, and a nitrogen-containing compound having an amine group and/or an imine group, all of the amine group and/or an imine group present in the nitrogen-containing compound, and at least a dihydrogen atom via the hydroxyl group The alkyl group and/or the alkoxyalkyl group-substituted nitrogen-containing compound is preferred. The number of the above substituents is 2 or more in the nitrogen-containing compound, and is substantially 6 or less. Examples of the melamine-based compound, the urea-based compound, the guanamine-based compound, the acetaminophen-based compound, the benzoguanamine-based compound, the glycoluril-based compound, the succinimide-based compound, and the ethylene-urea compound, and the amine group and And a compound having two or more hydrogen atoms of an imido group substituted with a methylol group or an alkoxymethyl group or both. The nitrogen-containing compound may, for example, be a melamine-based compound, a urea-based compound or a guanamine-based compound. a compound, an acetamide compound, a benzoguanamine compound, a glycoluril compound, an amber amide compound, an ethylene urea compound, etc., is reacted with fumarin in boiling water to form a methylol group, or more The lower alcohol, specifically, alkoxylated by reaction of methanol, ethanol, n-propanol, isopropanol, n-butanol or isobutanol. When the above-mentioned crosslinking agent uses the above-mentioned hydroxyalkyl group and/or alkoxyalkyl group and a condensation reaction product with a monohydroxymonocarboxylic acid, the effect of the shape of the lower part of the photoresist pattern can be improved (prevention of the foot shape). good. -32- (29) 1258635 The above monohydroxymonocarboxylic acid, in which a hydroxyl group and a carboxyl group are bonded to the same carbon atom' or two adjacent carbon atoms, is preferably prevented in the form of a foot. When a condensation reaction with a monohydroxymonocarboxylic acid is used, the monohydroxy carboxylic acid is condensed with a molar ratio of 0.01 to 6 moles, preferably 0.1 to 5 moles, per mole of the crosslinking agent before condensation. The use of the reactant obtained by the reaction is preferred because the effect of preventing the shape of the foot is obtained. In the first, second and third underlayer film forming materials of the present invention, the above-mentioned crosslinking agent may be used alone or in combination of two or more. Further, when necessary, a high light absorbing component, an acidic compound, a surfactant, and a second and third underlayer film forming material of the present invention may be added to the first underlayer film forming material and the embedding material according to the present invention. A highly light absorbing component, an acidic compound, or a surfactant may be added as necessary. The addition effect of the above-mentioned highly light-absorbing component is that the absorption characteristics of the exposure light are further improved. When the highly light-absorbing component has an absorption characteristic of the exposure light irradiated to the photoresist layer, it is possible to prevent the standing wave generated by the reflection of the exposure light from being reflected by the substrate, and scattering due to the difference in height between the surface of the substrate is not particularly limited. Such a substance is, for example, a water waking compound, a diphenyl ketone compound, a benzotriazole compound, a cyanoacrylate compound, an azo compound, a polyene compound, a quinone compound, Any of a master compound (preferably a diphenyl monolithic compound), an aspirite compound (a bisphenyl sub-system), an anthraquinone compound, or the like can be used. These may be used alone or in combination of two or more. Among them, an anthraquinone compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl 'alkoxyalkyl group, and a carboxyl group, a diphenyl macro compound, and a double The phenyl sub-synthesis compound and the monophenyl ketone-based compound preferably have at least one selected from the group consisting of -33 - (30) 1258635 because of their high absorption characteristics. Among them, particularly preferred are, for example, a lanthanide compound or a diphenyl macro compound. These may be used singly or in combination of two or more. The effect of the addition of the above acidic compound is that the prevention property of the foot is improved. Such acidic compounds include inorganic acids having an acid residue containing sulfur, organic acids or esters thereof, and compounds which generate an acid with an active light (an acid generator such as a salt). In the first underlayer film forming material and the embedding material of the present invention, 30 parts by mass of 100 parts by mass of the total solid content is blended, and preferably 20 parts by mass is used as the upper limit. The second and third underlayer film forming materials of the present invention are preferably from 1 to 30 parts by mass, preferably from 0.1 to 20 parts by mass, based on 100 parts by mass of the total solid content. If the amount is too small, the effect is not added. If the upper limit is exceeded, the undercut of the photoresist pattern is generated. The effect of the above surfactant is increased by the coating property of the underlying film material, and the embedding material is Improvement in coating properties and enhancement of embedding into the etching space. Such a surfactant is, for example, SURFLON SC-103, SR-100 (above, manufactured by Asahi Glass Co., Ltd.), ef-351 (manufactured by Tohoku Fertilizer Co., Ltd.), FLOURAD Fc-431, FLUORAD Fc-135 FLUORAD Fc- 98 > FLOURAD Fc- 430 ^ FLUORAD Fc- 176 (above, Sumitomo 3] y [manufactured by the company), MEGAFAC R09 (manufactured by Dainippon Ink Co., Ltd.) and other fluorine-based interface agents. The amount of the surfactant added is preferably in the range of 200 ppm which is less than the total solid content of the underlying film material. Next, the first circuit forming method of the present invention - 34 - (31) 1258635 will be described again with reference to Fig. 4. In the first circuit forming method of the present invention, first, the underlying film forming material for lithography of the present invention is used on the semiconductor substrate 1?1 in which the dielectric layer 101b is laminated on the substrate 1 1 1 a such as a germanium wafer. The underlayer film 102 is formed (lower film formation process (a)). Next, a photoresist layer 103 is formed on the underlayer film 102, and an exposure and development process is applied to the photoresist layer 103 to form a specific photoresist pattern 103 (photoresist pattern forming process (b)). The exposed portion of the underlying film 102 which is not covered by the above-described photoresist pattern type 1 4 is removed by dry etching (lower film patterning process (c)). The dielectric pattern 101b of the substrate 101 is etched to form a specific circuit pattern 105 (circuit pattern forming process (d)) by using the photoresist pattern 104 and the patterned lower film 1〇2 as masks. The underlayer film 102 and the photoresist pattern 104 remaining on the substrate 101 after the circuit pattern 105 is formed are simultaneously removed by the photoresist stripping liquid (lower film removing process (e)). The circuit forming method of the present invention is characterized in that: These processes (a) to (e) are included. The above circuit pattern 105 is, for example, embedded in a conductor material to form a circuit layer. The description of the method assumes the simplest circuit configuration, and is of course also applicable to a multilayer circuit structure in which the upper and lower layers are electrically connected by a via circuit. The construction of the method of the invention is illustrated by the necessary minimum. Moreover, the method is assumed to be a so-called Damascus process, and in the case of a multi-layer structure, a double damascene process is necessarily required. The dual damascene process is characterized in that a wiring groove called a trench is connected to a via hole. The order of formation is to form a trench first, then form a via hole, and conversely form a via hole first, and then form a -35- (32) 1258635 trench. The present invention can employ either of them. Next, a second circuit forming method of the present invention will be described with reference to Fig. 5. In the second circuit forming method of the present invention, first, the lower layer of the germanium-containing two-layer photoresist process of the present invention is used on the semiconductor substrate 201 formed by laminating at least the dielectric layer 201b on the substrate 201a such as a germanium wafer. The film forming material forms a photoresist underlayer film 202 (lower film forming process (a)). Next, a photoresist upper layer film 203 formed of a photoresist material is formed on the underlying film 202, and the photoresist upper layer film 203 is subjected to exposure and development processing to form a specific photoresist pattern 204 (upper photoresist pattern formation process) (b)). The exposed portion of the underlying film 202 not covered by the upper photoresist pattern 204 is removed by dry etching to form a lower photoresist pattern 205 (lower photoresist pattern forming process (c)). The upper layer resist pattern 204 and the lower layer resist pattern 205 are used as masks, and the dielectric layer 201b of the substrate 201 is etched to form a specific circuit pattern 206 (circuit pattern forming process (d)). The lower photoresist pattern 205 and the upper photoresist pattern 204 remaining on the substrate 201 after the circuit pattern 20 is formed are simultaneously removed by a photoresist stripping solution (photoresist pattern removing process (e)). The circuit forming method of the present invention is characterized by comprising these processes (a) to (e). The circuit pattern 206 is formed, for example, by embedding a conductor material to form a circuit layer. The description of the method assumes the simplest circuit configuration, and is of course also applicable to a multilayer circuit structure in which the upper and lower circuit layers are electrically connected by a via circuit. The composition of the method of the present invention is shown in the process of the minimum necessary -36- (33) 1258635. This method is assumed to be a so-called Damascus process, which is a multi-layer structure, which necessitates the use of a dual Damascus process. The dual damascene process is characterized in that a circuit trench called a trench is formed by connecting a via hole, and the formation order has a first trench formed, and then a via hole is formed, and a via hole is formed first, and then a trench is formed. The invention is applicable to either. Next, the third circuit forming method of the present invention will be described in more detail with reference to Figs. 6A to 6D and Figs. 7E to 7H. In the third circuit forming method of the present invention, first, as shown in FIG. 6A, the multilayer photoresist underlayer film of the present invention is used on the semiconductor substrate 301 in which the dielectric layer 30 lb is laminated on the substrate 3018 of the wafer or the like. Forming a material to form a thick film photoresist underlayer film 3〇2 (lower layer film formation process (Ο). As shown in FIG. 6B, an intermediate layer film 303 is formed on the underlying film 302 by spin-on glass material (intermediate layer) Film formation process (b)). Next, as shown in FIG. 6C, a photoresist upper film 3〇4 formed of a photoresist material is formed on the interlayer film 303, and an exposure and development process is performed on the photoresist upper film. Forming a specific photoresist pattern 305 (upper photoresist pattern formation process (c)). Next, as shown in FIG. 6D, the intermediate layer film 303 is dry-etched by the above-mentioned upper photoresist pattern 305 as a mask. An intermediate layer pattern 306 is formed (intermediate layer pattern forming process (d)). Next, as shown in Fig. 7E, the lower layer film 302 is processed by dry etching using the above intermediate layer pattern 306 as a mask to form a lower layer pattern 307. (Lower pattern formation process (e)) -37- (34) 1258635 Second, As shown in FIG. 7E, the dielectric layer 301b of the substrate 301 is etched by using the lower layer pattern 307 as a mask to form a specific circuit pattern 308 (circuit pattern forming process (Ο). Then, as shown in FIG. 7G, the circuit pattern is formed. The lower photoresist pattern 307 remaining on the substrate 301 after the type 308 is removed by a photoresist stripping solution (photoresist pattern removing process (g)). Finally, as shown in Fig. 7H, in the above circuit pattern 308, gas is used. The conductor material is deposited by a phase method or embedded in a conductor material to form a circuit layer 309 (circuit layer forming process (b)). The third circuit forming method of the present invention is characterized in that at least these processes (a) to ( g) The description of the method assumes the simplest circuit configuration, and of course applies to a multilayer circuit structure in which the circuit layers of the upper and lower layers are electrically connected by a via circuit. The composition of the method of the present invention is The process of showing the necessary minimum. This method is assumed to be a so-called Damascus process. When it is a multi-layer structure, it is necessary to adopt a dual damascene process. The double damascene process is characterized by: The circuit trench is connected to the via hole to form a 'forming sequence, first forming a trench, then forming a via hole, and conversely forming a via hole first, and then forming a trench. The present invention can be applied to any of them. 8A to 8D and 9E to 91 illustrate in more detail an example of the fourth circuit forming method (double damascene structure forming method) of the present invention. First, as shown in Fig. 8A, a low dielectric layer (interlayer insulating) is formed on the substrate 401. a layer 402 is formed on the low dielectric layer 402 and patterned. The patterned photoresist film 403 is selectively etched by a mask -38- (35) 1258635 low dielectric Body layer 402, followed by removal of photoresist film 403, as shown in FIG. 8B, forms a circuit trench 404. Next, on the surface of the low dielectric layer 402 on which the circuit trench 404 is formed, a barrier metal 405 is deposited on the inner surface of the circuit trench 404 to form copper and low dielectric embedded in the circuit trench 404. The adhesion of the bulk layer 402 while preventing the diffusion of the barrier metal film in the copper dielectric layer 402. Then, as shown in Fig. 8C, copper is buried in the circuit trench 404 by electroplating or the like to form the lower circuit layer 406. Next, the copper adhered to the surface of the low dielectric layer 04 and the residual barrier metal 405 at this time are removed by chemical honing (CMP), and the surface of the low dielectric layer 402 is planarized, and then laminated thereon. The first low dielectric layer 407, the first etch stop film 408, the second low dielectric layer 409, and the second etch stop film 4 10 (interlayer insulating layer forming process). Next, on the second etching stopper film 410, a reflection preventing film 4 1 1 is formed. A photoresist is applied to the anti-reflection film 4 1 1 , and a pattern for forming a via hole is formed to form a photoresist mask 412. Next, as shown in FIG. 8D, the photoresist mask 4 1 2 is etched to form a through-reflection prevention film 4 1 1 , a second etch stop film 410, a second dielectric layer 4〇9, and a first uranium stop layer. 40 8 and the first low dielectric layer 407 reach the via hole 4 1 3 on the surface of the lower circuit layer 406 (first etching space forming process). Then, after removing the photoresist mask 412 and the anti-reflection film 411, the embedding material for forming a double damascene structure of the present invention is applied to the second etch-stop film 4 1 如 as shown in FIG. 9E. The first etching space 4 1 3 is buried to form an embedding material layer 4 1 4 a, and an embedding material 4 14b is formed in the first etching space 4 1 3 (embedding process). -39- (36) 1258635, as shown in FIG. 9F, an anti-reflection film 415 which can be processed by dry etching is laminated on the embedding material layer 4 1 4 a, and a photoresist for trench formation is coated on the anti-reflection film 415. The illuminating pattern is applied to the photoresist layer and developed with an alkali developing solution to form a photoresist pattern 4 16 (photoresist pattern forming process). Next, the exposed portion of the anti-reflection film 4 1 5 which is not covered by the photoresist pattern 4 16 is processed by dry etching using the photoresist pattern 4 16 as a mask. Subsequently, the second uranium stop film 410 and the second low dielectric layer 4〇9 are etched using the photoresist pattern 416 to form a trench 417 as shown in Fig. 9C (second etching space forming process). Then, the embedding material layer 414a in the via hole 413 is completely removed with the stripping liquid together with the photoresist pattern 416 and the anti-reflection film 415 using a stripping solution. At this time, the shape of the dwelling is formed into a double damascene structure such as the groove 471 and the mesopores 413 of the ninth. Then, the via hole 413 and the trench 41 7 are embedded in copper, and a via circuit 418 and an upper circuit layer 419 are simultaneously formed as shown in Fig. 91. Thereby, the lower circuit layer 406 and the upper circuit layer 419 are realized by a multilayer circuit structure in which the via circuit 418 is electrically connected. The above description is directed to those who first form a via hole, but it is known that the trench is formed first. The above description is based on the process of forming the anti-reflection film 415 after the embedding process, and the process of forming the photoresist pattern 416 after the embedding process is provided, and the anti-reflection film processing with the photoresist pattern type 4 16 as a mask is provided. The process, but not the process of the invention, is not particularly necessary. When the anti-reflection film 415 is provided, the exposure light when the photoresist pattern 416 is formed can be suppressed, and the heating energy is adversely affected by the low dielectric layer 40 - (37) 1258635, which can more effectively prevent the occurrence of poisoning. . Each of the first circuit formation methods under the layer film removal process (e) 'the second circuit formation method of the photoresist pattern removal process (e), the third circuit shape method of the lower layer pattern removal process (g) And the above-mentioned photoresist stripping liquid used in the embedding material removing process (h) of the fourth circuit forming method is preferably at least one selected from the group consisting of water-soluble amines and quaternary ammonium hydroxides. . Among them, a preferred one is a photoresist stripping solution containing a quaternary ammonium hydroxide. The above water-soluble amine is preferably at least one selected from the group consisting of an alkanolamine and an alkylamine. The release agent containing such an amine-based release liquid may be further blended with a non-amine-based water-soluble organic solvent, water, an anti-corrosion agent, a surfactant, and the like. The non-amine-based water-soluble organic solvent is, for example, a sub-class such as dimethyl sulfene; a dimethyl group, a diphenyl group, a bis(2-hydroxyethyl) mill, a tetramethylene mill or the like; , N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrolidone, etc.; - lactones, 7-butyrolactone, 7-pentane vinegar, 5-valerolactone, 7-caprolactone, ε-caprolactone and other lactones; 1,3-dimethyl-2 Sedative D-ketone|, 1' 3 - ethyl 2- 2 - misoprostol, 1,3 -diisopropyl-2-imidazolidinone, etc.; ethylene glycol, B Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol , diethylene glycol • 41 - (38) 1258635 monoacetate, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, glycerin, 1,4-butanediol, 1,3-butanediol, 2,3- Polyols such as butanediol and derivatives thereof. These may be used alone or in combination of two or more. Further, in the method of the present invention, the process of contacting the underlayer film with ozone water and/or hydrogen peroxide may be carried out before the separation treatment. Ozone water is preferably dissolved in pure water by means of bubbling or the like by ozone gas. The ozone concentration may be between 1 ppm or more and the saturated concentration, and the hydrogen peroxide may be used in an aqueous solution having a concentration of 〇·1 to 60% by mass. The contact method includes a soaking method, a dipping method, a shower method, and the like. After the treatment is performed as described above, in the first circuit forming method, the removal performance of the underlying film and the photoresist film can be improved, and in the second and third circuit forming methods, the removal performance of the photoresist underlayer film and the photoresist upper film can be improved. Upgrade. In the first and fourth circuit forming methods of the present invention, the photoresist composition for forming the photoresist layer is not particularly limited, and the photoresist composition is usable, and the j-line, g-line, KrF excimer laser, and ArF of the mercury lamp are used. Quasi-molecular lasers, as well as photoresist compositions commonly used for exposure light such as F2 excimer lasers. Further, in the second circuit forming method of the present invention, the ruthenium-containing photoresist composition for forming the photoresist upper layer film can be used as described in the above-mentioned JP-A-2002-033257. In the third circuit forming method of the present invention, the photoresist composition for forming the photoresist upper layer film may be a conventional photoresist method for KrF, ArF, F2e excimer laser or electron beam. In the first to fourth circuit forming methods of the present invention, the exposure and development processes can be performed by a process commonly used in usual lithography. • 42 _ (39) 1258635 In the third circuit forming method of the present invention, various cerium-containing polymers can be used for the ruthenium oxide film material for forming the above intermediate layer. Among them, spin-on glass materials are suitable. Such a spin-on glass material is selected from (A) Si (OR1) a ( 〇R^) b ( OR3) c ( 〇R^) d (wherein R1, R2, R3 and R4 are each independently, and the number of carbon atoms is An alkyl group of 1 to 4 or a phenyl group, a, b, c and d are Osa s4, Osb < 4, Os cs4, 0^cU4, and an integer satisfying the condition of a + b + c + d = 4. a compound, (B) R5Si (OR6) e ( OR7) f ( 〇R5) £ (wherein R 5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 6 , R 7 and R 8 are each a carbon number of 1 to 3 alkyl or phenyl, e, f and g are Ose $3, , 〇^g < 3, and an integer satisfying the condition of e + f + g = 3.) Compound 5 and (C) R9R10Si (OR11) b ( OR12 ) i (wherein R 9 and R 1 G are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 11 and R 12 are each an alkyl group having 1 to 2 carbon atoms or a phenyl group; h and I are 0 sh 2 2 And at least one compound of the compound satisfying the condition of h + ^2.) is obtained by hydrolysis of an acid by the action of an acid in the presence of water. -43 · (40) 1258635 The compound of the above (A) is, for example, tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane, tetrabutoxydecane, tetraphenoxydecane, trimethoxyl Ethoxy decane, dimethoxydiethoxy decane, triethoxy monomethoxy decane, trimethoxy monopropoxy decane, monomethoxy tributoxy decane, monomethoxy triphenyl Oxydecane, dimethoxydibutoxydecane, triethoxy monobutoxydecane, diethoxydipropoxydecane, tributoxymonopropoxydecane, dimethoxylethane Oxylobutoxy decane, diethoxy monomethoxy monobutoxy decane, diethoxy monopropoxy monobutoxy decane, dipropoxy monomethoxy monoethoxy decane, Dipropoxy monomethoxy monobutoxydecane dipropoxy monoethoxy monobutoxydecane, dibutoxy monomethoxy monoethoxy decane, dibutoxy monoethoxy single a tetraalkoxy decane such as propoxy decane, monomethoxy monoethoxypropoxy monobutoxy or the like, wherein tetramethoxy decane, tetraethoxy decane The preferred such oligomers. The compound of the above (B) is, for example, trimethoxy decane, triethoxy decane, tripropoxy decane, triphenyloxydecane, dimethoxy monoethoxy oxime, diethoxy monomethoxy Base sand, dipropoxy monomethoxy sand, dipropoxy monoethoxy decane 'diphenoxy monomethoxy decane, diphenoxy monoethoxy sand, diphenoxy Monopropoxy sand, methoxyethoxypropoxy-5, monopropoxydimethoxydecane, monopropoxydiethoxydecane, monobutoxydimethoxydecane, Monophenoxy diethoxy decane, methyl trimethoxy sand, methyl diethoxy oxime, methyl tripropoxy 5 cesium, ethyl trimethoxy shixi, ethyl dipropyl Oxygen sand yard, ethyl triphenoxy sand court, propyl trimethoxy sand court, propyl diethoxylate sand garden, propyl triphenyloxy 5 Xiyuan, butyl trimethoxy decane, butyl Triethoxy decane, butyl tripropoxy decane, butyl-44 - (41) 1258635 triphenyloxydecane, methyl monomethoxydiethoxydecane, ethyl monomethoxydiethoxy Base decane Diethoxy decane, butyl monomethoxydiethoxy decane 'methyl monomethoxy dipropoxy decane, methyl monomethoxy diphenoxy decane, ethyl mono methoxy Propoxydecane, ethyl monomethoxydiphenoxydecane, propyl monomethoxydipropoxydecane, propyl monomethoxydiphenoxydecane, butyl monomethoxydipropoxy Baseline, butyl monomethoxydiphenoxydecane, methylmethoxyethoxypropoxydecane, propylmethoxyethoxypropoxydecane, butylmethoxyethoxypropoxydecane , methyl monomethoxy monoethoxy monobutoxy decane, ethyl monomethoxy monoethoxy monobutoxy decane, propyl monomethoxy monoethoxy monobutoxy decane, butyl The monomethoxymethoxy monoethoxy monobutoxydecane or the like is preferably trimethoxydecane or triethoxysilane. The compound of the above (C) is, for example, dimethoxydecane, diethoxydecane, dipropoxydecane, diphenoxydecane, methoxyethoxydecane, methoxypropoxydecane, A Oxyphenoxydecane, ethoxy propoxy decane, ethoxyphenoxydecane, methyl dimethoxy decane, methyl methoxy ethoxy shixi, methyl monoethoxy oxime Institute, methyl methoxypropoxy sand court, methyl methoxy phenoxy decane, ethyl di propoxy decane, ethyl methoxy propoxy oxa sylvestre, ethyl diphenoxy 5 Home, propyl dimethoxy sand, propyl methoxy ethoxy decane, propyl ethoxy propoxy decane, propyl diethoxy decane, propyl diphenoxy decane, butyl Dimethoxydecane, butyl methoxy ethoxy decane, butyl diethoxy decane, butyl ethoxy propoxy decane, butyl dipropoxy decane, butyl methyl phenoxy decane, dimethyl Dimethoxy decane, dimethyl methoxy ethoxy decane, dimethyl diethoxy decane, dimethyl • 45 - (42) 1258635 diphenoxy decane, dimethyl Oxypropoxydecane, dimethyldipropoxydecane, diethyldimethoxydecane, diethylmethoxypropoxydecane, diethyldiethoxypropoxydecane, dipropyl Dimethoxy decane, dipropyl diethoxy decane, dipropyl diphenoxy decane, dibutyl dimethoxy decane, dibutyl monoethoxy decane, dibutyl dipropoxy Decane, dibutylmethoxyphenoxydecane, methylethyldimethoxydecane', methylethyldiethoxydecane, methylethyldipropoxydecane, methylethyldiphenoxydecane , methyl propyl dimethoxy decane, methyl propyl diethoxy decane, methyl butyl dimethoxy decane, methyl butyl diethoxy decane, methyl butyl di propoxy decane , methyl ethyl ethoxy propoxy decane, ethyl propyl dimethoxy decane, ethyl propyl methoxy ethoxy decane, dipropyl dimethoxy decane, dipropyl methoxy Ethoxy decane, propyl butyl dimethoxy decane, propyl butane diethoxy decane, dibutyl methoxy propoxy decane, butyl ethoxy propoxy decane, etc. Among them, dimethyl decane, diethoxy decane, and methyl dimethoxy decane are preferred. The etching gas for dry etching of the intermediate layer spin-coated glass material is a gas containing a ruthenium IJ carbon-based gas as a main component. The etching gas for dry etching of the underlayer film material of the present invention is a gas containing a gas as a main component. In the fourth circuit forming method of the present invention, the conductor material for the circuit layer is preferably Cu, and the Cu alloy, Al, Al alloy or the like may be used in addition to Cu. The embedding circuit layer is formed by electroplating or the like, but is not particularly limited.

Materials which can be used for the above low dielectric layer are carbon doped oxide (Si〇c), methyl sesquioxanes (MSQ), hydroxy sesquioxanes (HSQ-46 - (43) 1258635) Low dielectric material. The above-mentioned carbon-doped oxide-based low dielectric material 'specifically, BLACK DIAMOND (trade name) manufactured by Apllied Materials Co., Ltd., CORAL (trade name) of Novelus Systems, and Aurora (trade name) manufactured by Sakamoto AS Co., Ltd. )Wait. Further, the above-mentioned low dielectric material of the methyl sesquioxane system, specifically, Tokyo Chemical Industry Co., Ltd., 〇CD T- 9",, 〇CD T - 11", 〇CL· T - 31",,,〇CL·T—37〃,, '〇CL T-39", the name of the product sold. The above-mentioned hydroxy sesquioxane-based low dielectric material, specifically, Tokyo Toka Chemical Industry Co., Ltd., ', 〇CD Τ 12", 〇CL Τ 32 32" . In the fourth circuit forming method of the present invention, the low dielectric layer may be formed on the circuit layer, or a barrier film (etch stop layer: SiN, SiC, SiCN, Ta, TaN, etc.) may be formed on the circuit layer. on. The calcination temperature of the low dielectric layer is usually hard baked at above 350 °C. The photoresist layer may be subjected to a lithography method using a photoresist for a mercury lamp, a g-line, a KrF excimer laser, an ArF excimer laser, an F2 excimer laser, or an electron beam (EB: Electron Beam). material. In the fourth circuit forming method of the present invention, if necessary, the above-mentioned antireflection film can be used, and a commercially available material which can be removed by a conventional CF4 etching gas and a 2 + 〇2 etching gas can be used. The reflection preventing film absorbs the exposure light to prevent it from entering the lower layer. Commercially available anti-reflection film materials are available from Tokyo Chemical Industry Co., Ltd. as ''SWK-EX1D55",,, SWK-EX3", 'SWK-EX4",, SWK-T5D6CT, vv SWK-T7 " The materials sold by the trade name, Brewer Science, etc. - 42." , , , DUV — 44", ', -4/- (44) 1258635 ARC— 28〃 , " ARC- 29" Materials sold by Shipley are sold under the trade names of ''AR' 3', AR' 19', etc. When the antireflection film is used, as described above, the second etching space is formed, and after the embedding material in the first etching space is removed, the photoresist film and the antireflection film are removed. These anti-reflection films are usually removed by an oxygen plasma polishing treatment. At this time, the damage caused by the low dielectric layer is not good. Therefore, in the present invention, the removal treatment of the anti-reflection film is preferably carried out by removing or peeling off the embedding material layer of the lower layer of the anti-reflection film. In particular, in the case of a low dielectric layer hydroxy sesquioxane-based material, it is treated by plasma irradiation of an inert gas such as He or Ar to improve the surface of the low dielectric layer. After the surface modification treatment, the residual anti-reflection film and the photoresist pattern can be removed by the oxygen plasma treatment without causing damage to the low dielectric layer. Embodiments of the invention are described below. The following examples are merely illustrative of the invention and the invention is in no way limited thereto. The following Examples 1 to 5 and Comparative Example 1 relate to a first underlayer film forming material and a circuit forming method of the present invention. (Examples 1 to 4) The following resin compositions (A), (B), (C) and (D) were prepared as the underlayer film forming material. (A) A resin composition obtained by dissolving a resin component of ethyl p-styrenesulfonate in γ-butyrolactone/ethyl lactate (2:8), and a resin composition having a solid content concentration adjusted to 6% by weight. -48 - (45) 1258635 (B ) A resin component obtained by dissolving ethyl p-styrenesulfonate: hydroxyethyl acrylate (-5:5), and CYMEL® 72 equivalent to 2% by weight of the resin component ( A solvent composed of a tetramethylol glycoluril manufactured by Mitsui Cyanamid Co., Ltd. in a solvent of ethyl lactate, and a solid content concentration adjusted to 6% by weight.

(C) Solving a solvent formed by dissolving ethyl p-styrenesulfonate/9-hydroxy decyl acrylate (5:5) in r-butylpropyl ester/ethyl lactate (h 8) to prepare a solid A resin composition having a component concentration of 6 wt%. (D) Dissolving a resin component of ethyl p-styrenesulfonate / hydroxyethyl acrylate / 9-hydroxy decyl acrylate (4:3:3), equivalent to 20% by weight of the resin 2CYMEL 1172 (Mitsui Cyanamid ( Manufactured by tetramethylol glycoluril), and a solvent equivalent to 100% of the solid content of the above, MEGAFAC R08 (a fluorine-based surfactant prepared by Dainippon Ink Co., Ltd.) was adjusted in a solvent made of ethyl lactate. A resin composition having a solid content concentration of 6% by weight. Each of the resin compositions of (A) (B) (C) (D) was applied onto a semiconductor substrate, and subjected to a heat treatment for 20 seconds at TC for 90 seconds to form a film having a film thickness of 2000 Å. Coating TDUR-P630 (Tokyo should The photoresist (manufactured by the chemical industry) is heat-treated at 120 ° C for 90 seconds on these underlying films to form a photoresist layer having a film thickness of 5000 angstroms. The photoresist layer is sequentially exposed to light after exposure and exposure. (11 ° ° C, 90 seconds), development processing, forming a 250 nm photoresist pattern. The photoresist pattern obtained above does not cover the exposed portion of the underlying film 'dry type using fluorocarbon etching gas In the above-mentioned photoresist pattern, the underlying film is masked by the same pattern as the light-49-(46) 1258635 resistance pattern, and the underlying substrate dielectric layer is etched to form a trench or a via hole. Circuit structure. After forming the circuit structure as described above, the substrate is immersed in a mixed solvent of dimethyl sulfoxide and monoethanolamine (mixing ratio = 7:3) at 1 ° C for 20 minutes to remove the photoresist pattern. Type and underlayer film. The surface of each substrate after peeling treatment of the underlying film was observed by a scanning cat microscope. The resolution of the circuit structure pattern was confirmed. As a result, it was confirmed that when any of the underlayer film materials of (A)(B)(C)(D) was used, a rectangular pattern having excellent dimensional controllability and a good cross-sectional shape was obtained. Example 5) In the resin composition (C), a photoacid generator TPS-109 (manufactured by Green Chemical Co., Ltd.) was added in an amount of 3% by weight based on the amount of the resin component, and another resin composition was prepared ( C2) A circuit configuration was formed as in Example 1 except that the resin composition (C2) was used. As a result, a circuit configuration having an excellent dimensional control property and a rectangular pattern was obtained. (Comparative Example 1) Cross-linking with a main component The film material (product name SWK-EX3 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto a semiconductor substrate and heat-treated at 200 ° C for 90 seconds to form a film having a film thickness of 2000 Å. A large photoresist composition (trade name: TDUR-P630, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was heat-treated at 120 ° C for 90 seconds on the underlayer film to form a photoresist layer having a film thickness of 5000 angstroms. Pre-exposure, post-exposure heating -50 - (47) 1258635 (11 (TC, 90 seconds), development processing, forming a 250 nm photoresist pattern. The exposed portion of the underlying film that is not covered by the photoresist pattern as described above is a dry uranium using a fluorocarbon-based etching gas. In the above-mentioned photoresist pattern, and under the same pattern as the photoresist pattern layer, the underlying film is masked, and the underlying dielectric layer of the substrate is etched to form a circuit structure such as a trench or a via hole. After forming the circuit structure, the photoresist pattern and the underlying film remaining on the substrate are removed by grinding with 〇2. The surface of each substrate after being polished and removed is observed by a scanning cat microscope, and the structural patterns of each circuit are evaluated. Resolution. As a result, the formation of the circuit structure causes corrosion on the surface of the dielectric layer, which is presumed to cause defects in the device characteristics after the formation of the circuit layer. After the above circuit configuration was formed, the substrate was immediately immersed in the stripping solution used in the above examples under the same conditions, and the remaining underlayer film could not be removed. The following Examples 6 to 10 and Comparative Examples 2 to 4 relate to the second underlayer film forming material and circuit forming method of the present invention. (Examples 6 to 9) The following resin compositions of (A), (b), (C) and (D) were prepared as a lower film forming material. (A) A resin composition obtained by dissolving a resin component of ethyl p-styrenesulfonate in a solvent of r-butyl acetate/ethyl acetate (2:8), and a resin composition having a solid concentration adjusted to 6 wt%. (B) Dissolving ethyl p-styrenesulfonate: a resin component of hydroxyethyl acrylate (=5:5) m and -20% by weight of the resin component -51 - (48) 1258635 CYMEL 1172 (Mitsui A resin composition of tetrahydroxymethyl glycoluril produced by Cyanamid Co., Ltd. in a solvent of ethyl lactate, and a solid content concentration adjusted to 6% by weight. (C) Solvent dissolved in ethyl p-styrenesulfonate: 9-hydroxy decyl acrylate (=5:5) in r-butyrolactone/ethyl lactate (2:8), solid The composition of the component was adjusted to a resin composition of 6% by weight. (D) A resin component obtained by dissolving ethyl p-styrenesulfonate: hydroxyethyl acrylate: 9-hydroxydecyl acrylate (=4:3:3), equivalent to 20% by weight of the resin, CYMEL 1172 (Mitsui Cyanamid (tetramethylol glycoluril) manufactured by Cyanamid, and MEGAFAC R08 (fluorine-based surfactant manufactured by Dainippon Ink Co., Ltd.) in an amount equivalent to 1% by mass of the above two components in ethyl lactate The solvent was prepared, and the solid content was adjusted to a resin composition of 6% by weight. Each of the resin compositions of (A) (B) (C) (D) was applied onto a semiconductor substrate, and heat-treated at 200 °C for 90 seconds to form an underlayer film having a film thickness of 3,000 Å. These underlying films were coated with a photoresist composition containing ruthenium, and heat-treated at 1 〇 〇 °c for 90 seconds to form a photoresist upper film having a film thickness of 1,500 Å. The photoresist upper layer is exposed, developed, and formed into an upper photoresist pattern. The exposed portion of the underlayer film which is not covered by the upper photoresist pattern is removed by dry etching using a fluorocarbon-based etching gas to obtain a lower photoresist pattern. The upper layer photoresist pattern and the lower layer photoresist pattern are used as masks, and the underlying dielectric layer of the substrate is etched to form a circuit structure such as a trench or a via hole. After forming the circuit structure as described above, the substrate was immersed in a mixture of dimethyl sulfoxide and monoethanolamine in a mixed solvent of -52-(49) 1258635 (mixing ratio of 2:7:3) for 20 minutes to remove the upper layer. Photoresist pattern and lower photoresist pattern.

The surface of each substrate after the release treatment of the underlayer film was observed by a scanning microscope, and the surface state of each substrate was evaluated. As a result, it was confirmed that when any of the underlayer film materials of (A) (B) (C) (D) was used, the residue of the underlayer film and the upper photoresist film was not observed, and the removal was sufficiently performed. (Example 10) Each of the resin compositions of the above (A) (B) (C) (D) was applied onto a semiconductor substrate, and heat-treated at 200 ° C for 90 seconds to form a film thickness of 300 Å. An underlayer film. The photoresist composition containing ruthenium was coated on these underlayer films, and heat-treated at 1 Å for 90 seconds to form a photoresist upper film having a film thickness of 150 Å. The upper film of the photoresist is subjected to exposure and development processing to form an upper photoresist pattern. As described above, the exposed portion of the underlying film which is not covered by the upper photoresist pattern is removed by dry etching using a fluorocarbon-based etch gas to obtain a lower photoresist pattern. The substrate at this stage was immersed in a mixture of dimethyl sulfoxide and monoethanolamine (mixing ratio = 7:3) for 10 minutes to remove the upper photoresist pattern and the lower photoresist pattern. type.

The surface of each substrate after the release treatment of the underlayer film was observed by a scanning microscope, and the surface state of each substrate was evaluated. As a result, when any of the underlayer film materials of (A) (B) (C) (D) was used, the residue of the upper film and the lower film was not observed, and the rework processing of the substrate was confirmed to be practical. -53- (50) 1258635 (Comparative Example 2) A circuit was formed as in the above Examples 1 to 4 except that a composition obtained by dissolving hexamethoxymethylated melamine in propylene glycol monomethyl ether acetate was used to form an underlayer film. Constructed on a semiconductor substrate. After forming the circuit structure as described above, the substrate was immersed in a mixed solvent of dimethyl sulfoxide and monoethanolamine (mixing ratio = 7:3) at 10 ° C for 20 minutes, and the upper photoresist pattern could not be removed. Lower photoresist pattern. (Comparative Example 3) An upper photoresist pattern and a lower photoresist were formed as in the above Example 1 except that a composition obtained by dissolving hexamethoxymethylated melamine in propylene glycol monomethyl ether acetate was formed to form an underlayer film. Graphic type. The substrate of this stage is separated from the substrate by the mixing ratio of dimethyl sulfite and monoethanolamine = 7:3). The TC is immersed for 20 minutes, and the upper photoresist pattern and the lower photoresist pattern cannot be removed. (Comparative Example 4) In the above Comparative Examples 2 and 3, the removal treatment of the substituted photoresist peeling liquid was carried out by the removal treatment by the plasma polishing. After the surface of each substrate after the treatment, the composition of the photoresist was contained. The upper layer of the photoresist pattern film is degraded into a residue. Therefore, in order to peel off the residue, the substrate is immersed in the alkali stripping solution, but it cannot be removed. Examples 11 to 15 and Comparative Examples 5 and 6 below are related. The third underlayer film forming material and circuit forming method of the present invention - 54 - (51) 1258635 (Examples 11 to 14) The following (A), (B), (c) and (D) resin resins are prepared as The underlayer film forming material. (A) The resin component obtained by dissolving ethyl p-styrenesulfonate, the solvent formed by r-butyrolactone/ethyl lactic acid (2:8), adjusted to a solid concentration of 6 wt% Resin composition. (B) Dissolving p-acetophenone sulfonic acid ethyl acetonate: acrylic acid via base B (=5: 5) The resin component formed and CYMEL1172 (tetramethylol glycoluril manufactured by Mitsui Cyanamid Co., Ltd.) equivalent to 2% by weight of the resin component, a solvent formed by ethyl lactate, and a solid component A resin composition having a concentration adjusted to 6% by weight. (C) A resin component obtained by dissolving ethyl p-styrenesulfonate: acrylic acid 9 monohydroxy vinegar (=5:5), in 7-butane vinegar/lactate B The solvent formed by vinegar (2:8), the resin composition whose solid concentration is adjusted to 6% by weight. (D) Dissolved ethyl p-styrenesulfonate: hydroxyethyl acrylate: 9-hydroxydecyl acrylate (=4) : 3: 3) The resin component formed is equivalent to 20% by weight of the resin, CYMEL 1 172 (tetrakis methyl hydroxyurea manufactured by Mitsui Cyan amid), and the amount of solid components corresponding to the above two 100,000 ppm of MEGAFAC R08 (a fluorine-based surfactant manufactured by Dainippon Ink Co., Ltd.), and a resin composition adjusted to a solid concentration of 6 wt% in a solvent made of ethyl lactate. On the other hand, as shown in Fig. 10A, Forming a first resistance formed by the SiN film on the substrate 502 on which the copper circuit layer 501 is formed. Layer 5 03 is used as the first layer, and the first low dielectric layer 504 formed of a low dielectric material (manufactured by Tokyo Chemical Industry Co., Ltd.: trade name 一CD-T12) is used as the first layer. In the second layer, the second barrier layer 505 formed by the S1N film is formed as the third layer, and the second dielectric layer (the Tokyo Chemical Industry Co., Ltd. product name: CD-T12) is formed into the second layer. The low dielectric layer 506 is used as the fourth layer. Next, as shown in FIG. 10B, the photoresist layer 507 is formed on the second low dielectric layer 506 to form the photoresist pattern 508 by lithography. With the obtained photoresist pattern 508 as a mask, via holes 509 penetrating the first to fourth layers and communicating with the copper circuit layer 501 are formed. After the via hole 509 is formed, the photoresist pattern 508 is removed.

As shown in FIG. 10C, the resin composition of the above (A) (B) (C) (〇) is formed on the second low dielectric layer 506 after forming the via hole 509 and removing the photoresist pattern 508. After coating, the above-mentioned via holes were buried, and then heat-treated at 200 ° C for 90 seconds to form a film 510 having a film thickness of 3 000 Å on the second low dielectric layer. On the underlayer film 5 10, a resin composition of a spin-coated glass material as a main component was applied to form an interlayer film 51 of a film thickness of 150 Å. Further, on the intermediate layer film 51 1 , a photoresist composition (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name: TArF - P607 1 ) was applied, and heat-treated at 120 ° C for 90 seconds to form a film thickness of 400 nm. The film is 512 above the meter. Next, the upper film 512 is subjected to exposure, post-exposure heating (120 ° C, 90 seconds), and subjected to development processing to form an upper layer photoresist pattern 5 1 3 for groove formation. The intermediate layer film pattern 513 is used as a mask, and the intermediate layer film 51 is processed by using a fluorocarbon-based etching gas to obtain an interlayer film pattern. Then, the intermediate layer film pattern is used as a mask, and an oxygen-based etching gas is used, and the lower layer film 510 is formed into the lower layer film 510 as described in FIG. The resistance pattern is used to form the final photoresist pattern of the trench. At this time, the pattern of the photoresist pattern due to the adverse effect of poisoning was not observed by the scanning electron microscope, and the damage of the low dielectric layer constituting the trench was not observed. The circuit layer forming process system is generally formed, and then the above-mentioned final photoresist pattern (lower photoresist pattern) is used as a mask for the second low dielectric layer 516, as shown in FIG. The groove of the specific pattern of the second barrier layer 505 is 5 1 5 . Then, copper is embedded in the via hole 507 and the trench 5 15 to form a multi-layer circuit structure. In the present embodiment, it is assumed that the pattern of the patterning failure is confirmed after the final photoresist pattern type 51 is obtained, and the photoresist pattern removing process required for the reworking is carried out as follows. Soaking the substrate having the above-mentioned lower photoresist pattern 5 1 4 in a photoresist stripping solution prepared by adjusting a mixed solvent of dimethyl sulfoxide and monoethanolamine (mixing ratio = 7 : 3 ) at 10 ° C 5 10 minutes, stripping treatment of the photoresist pattern. After the peeling treatment, the surface of the substrate was observed by a scanning microscope, and when any of the above resin compositions (A) to (D) was used as the underlayer film material, the residue of the photoresist pattern was not present, and the photoresist pattern was confirmed. The peeling removal has been carried out. There is also no observation of damage to the low dielectric layer 506 caused by the photoresist stripping treatment. (Example 1 5) In the resin composition of the above (C), a photoacid generator TPS-109 (manufactured by Green Chemical Co., Ltd.) was added in an amount of 3% by weight based on the amount of the resin component, and a resin composition was prepared. (C 2 ). A photoresist pattern was formed as in Example 1 except that the resin composition (C 2 ) -57-(54) 1258635 was used. As a result, a rectangular photoresist pattern excellent in size controllability can be obtained. It was confirmed that the influence of poisoning from the low dielectric layer can be suppressed by the underlayer film material of the present invention. Further, when the surface of the low dielectric layer was observed by a scanning microscope after the photoresist pattern peeling treatment, the residue of the resist pattern was not observed on the surface of the substrate after the peeling removal treatment, and it was confirmed that the removal was sufficiently performed. There is also no damage to the low dielectric layer. (Comparative Example 5) The resin composition of hexamethoxymethylated melamine in propylene glycol monomethanol acetate was dissolved to form an underlayer film material, which was removed as a lower layer pattern by 〇2 plasma polishing treatment, as in the above embodiment. , the formation of the photoresist pattern, and the stripping removal. As a result, poisoning occurs in the groove pattern with a photoresist pattern, and a portion in which a pattern image cannot be formed is produced. And the stripping treatment of the pattern by the 电2 plasma grinding causes serious damage in the dielectric layer. (Comparative Example 6) In the above Comparative Example 5, the photoresist stripping liquid used in the above examples was removed as a lower layer type. As a result, the pattern cannot be removed. In the following Examples 1 to 2 1, Comparative Examples 7 and 8 relate to the embedding material of the present invention and the fourth circuit forming method. (Examples 16 to 19) g The following resin compositions (A), (B), (C) and (D) were used as embedding materials. -55 > (55) 1258635 (A ) A solvent prepared by dissolving a resin component of ethyl p-styrenesulfonate in r-butyrolactone/ethyl lactate (2:8), and the solid concentration was adjusted to 6 % by weight of the resin composition. (B) a resin component obtained by dissolving ethyl p-styrenesulfonate: hydroxyethyl acrylate (=5:5), and CYMEL 1 172 (manufactured by Mitsui Cyanamid Co., Ltd.) in an amount equivalent to 20% by weight of the component of the resin composition Tetramethylol glycoluril was added to a solvent of ethyl lactate to adjust a resin composition having a solid concentration of 6 wt%. (C) a solvent obtained by dissolving a mixture of p-styrenesulfonate/9-hydroxydecyl acrylate (5:5) in 7-butpropyl ester/ethyl lactate (2:8), solid content The concentration was adjusted to 6% by weight of the resin composition. (D) A resin component obtained by dissolving ethyl p-styrenesulfonate/hydroxyethyl acrylate/acrylic acid 9-hydroxy oxime ester (4:3:3), equivalent to 20% by weight of the resin, CYMEL 1 172 (Mitsui Cyanamid (tetramethylol glycoluril) manufactured by Cyanamid, and 100 parts by mass of the above-mentioned solid content of MEGAFAC R08 (a fluorine-based surfactant prepared by Otsuka ink) is formed by ethyl lactate. The solvent was adjusted to have a resin composition having a solid concentration of 6 wt%. On the other hand, on the substrate on which the Cu layer is formed, a barrier layer formed by the first layer of the S?N film and a second layer of the low dielectric layer (OCD-T12: manufactured by Tokyo Yinghua Industry Co., Ltd.) are sequentially formed. ), a barrier layer formed of a third layer of SiN, and an interlayer insulating layer of a fourth layer of a low dielectric layer (OCD - T12; manufactured by Tokyo Ohka Kogyo Co., Ltd.). A photoresist composition (manufactured by Tokyo Ohka Kogyo Co., Ltd.: trade name: TDUR - P630) was applied onto the interlayer insulating layer, and heat-treated at 120 ° C for 90 seconds to form a photoresist layer having a film thickness of 5000 Å. The photoresist layer was sequentially exposed, exposed to -59-(56) 1258635, heated (110 ° C, 90 seconds), and developed to form a 250 nm photoresist pattern. The photoresist pattern is used as a mask, and the interlayer insulating layer is etched to form a via hole that communicates with the Cu layer. Coating the resin compositions (A) to (D) on the interlayer insulating layer after the removal of the photoresist pattern to form an embedding material layer on the interlayer insulating layer while embedding the embedding material in the interlayer Inside the hole. Then, it was calcined at 2 Torr: for 90 seconds. A photoresist composition (TDUR-P630: manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto the embedding material layer, and a photoresist layer having a film thickness of 4 Å was formed by heat treatment at 9 (TC for 90 seconds). The photoresist layer is exposed to light, heated after exposure (110 ° C, 90 seconds), and then subjected to development processing to form a photoresist pattern for trench formation. At this time, the shape of the trench is formed by a photoresist pattern. Scanning electron microscopy was used to observe the results. When using any of the embedded materials (A) to (D), there was no pattern defect due to the adverse effects of poisoning. For the material layer, the substrate is immersed in a mixed solvent of dimethyl sulfoxide and monoethanolamine (mixing ratio = 7:3) in 1 〇〇 art for 2 minutes, and stripped and removed. The residue was confirmed by a scanning electron microscope. When any of the embedding materials (A) to (D) was used, no residue was observed on the substrate or the plate, and no damage was observed in the low dielectric layer. Example 20) Sealing the embedding material of the resin composition (c) of the above-mentioned Example 18, -60 - ( 57) 1258635 A double damascene structure is formed as in the above embodiment except that the photoacid generator TPS-1 09 (manufactured by Green Chemical Co., Ltd.), which is equivalent to 3% by weight of the resin component, is blended. No pattern defects caused by adverse effects of poisoning. Also, no residue on the substrate after stripping treatment (Example 2 1 )

In Example 18 using the above-mentioned resin composition (C), an anti-reflection film (manufactured by Tokyo Ohka Kogyo Co., Ltd.: trade name SWK-9L) was formed as an intermediate layer with the photoresist layer, and double was formed under exactly the same conditions. Damascus structure. At this time, the pattern of the groove is formed by a photoresist pattern, and there is no pattern defect caused by the adverse effect of poisoning. Moreover, the residue on the substrate after the peeling treatment was not confirmed. (Comparative Example 7)

The embedding material is composed of a resin composition in which hexamethoxymethylated melamine is dissolved in propylene glycol monomethyl ether acetate, and the embedding material layer after use and the embedding material in the second etching space are removed by 〇2 In addition to the plasma sanding treatment, a double damascene structure was formed as in the above embodiment. As a result, the groove is poisoned by the photoresist pattern, and a portion incapable of forming a pattern image is generated. (Comparative Example 8) A spin-on glass material (manufactured by Tokyo Chemical Industry Co., Ltd.: trade name OCD-T 1 2) was used as an embedding material, and the embedding material layer and the second etching space were used -61 - ( 58) The removal of the embedding material of (58) 1258635 is carried out in addition to the 1% by weight buffered hydrofluoric acid aqueous solution, forming a double damascene structure as in the above embodiment. As a result, poisoning occurs in the pattern of formation of the groove, and a portion in which the pattern image cannot be formed is generated. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing a circuit formation method of a dual damascene process using a conventional embedding material, and a 1D to 1D process diagram formed by a circuit configuration using lithography. The second drawing is for explaining the circuit formation method of the latter half of Fig. 1 '''''''''''''' Fig. 3 is a view showing the poisoning phenomenon occurring when a double damascene structure is formed in a low dielectric layer, and the poisoning phenomenon does not occur in the 3 lanthanum system, and the top view of the important portion of the saturated spatial pattern subjected to patterning is performed. A top view of an important part of the etched space pattern that causes poisoning, and a diagram showing the first circuit forming method using the first underlayer film forming material of the present invention, the 4 Α to π system utilizing micro The circuit structure of the shadow is formed into a process map. Fig. 5 is a view showing a second circuit forming method using the underlayer film forming material (second underlying film material) for the ytterbium-containing two-layer photoresist process of the present invention, and the circuit structure using lithography by 5 Α to 5 Ε Form a process map. Figure 6 is a view showing a third circuit forming method for forming a material for the lower layer S 多层 of the multilayer photoresist process of the present invention (through the second 暦臆 ψ, 丨 _., 弟 卜 层 层 枓), ' 62 ^ (59) 1258635 6 A to 6D is a circuit that uses lithography to form the first half of the process diagram. Fig. 7 is a view showing a third circuit forming method using the underlayer film forming material (third underlayer film material) for the multilayer photoresist process of the present invention, and 7E and 7F are followed by the use of lithography in Fig. 6D. The second half of the circuit is formed. Fig. 8 is a view showing a circuit forming method (fourth circuit forming method) of a double damascene process using the embedding material of the present invention, and 8A to 8D are process diagrams for forming a circuit using lithography. Fig. 9 is a view for explaining a circuit formation method subsequent to the latter half of Fig. 8, and a circuit configuration forming process using lithography subsequent to Fig. 8 of 9E to 91. Fig. 1 is a view showing a third circuit forming method for forming a double damascene structure using the underlayer film forming material (third underlayer film material) for a multilayer photoresist process of the present invention, 10A to 10E The process map to form a double Damascus structure. Main components comparison Table 1 Substrate 2 Interlayer insulating film layer 3 Photoresist film 4 Circuit trench 5 Barrier metal 6 Lower circuit layer 7 First low dielectric layer -63 - 1258635 (60) 8 9 10 11,14 12 13 15 16 17 101a , 201a , 301a 101b , 201b , 301b 101 , 201 , 301 102 , 202 , 302 103 104 , 204 , 305 105 , 206 , 308 203 , 304 205 303 306 309 309 40 1 402 First etching stop Film second low dielectric layer second etch stop film photoresist mask via hole embedding trench, second etch space via layer upper layer circuit layer substrate dielectric layer semiconductor substrate underlayer film photoresist layer photoresist pattern circuit diagram Type photoresist upper film lower layer photoresist pattern intermediate layer film middle layer pattern lower layer pattern circuit layer substrate low dielectric layer -64 (61) 1258635 403 photoresist film 404 circuit trench (trench) 405 barrier metal 406 lower layer circuit Layer 407 first low dielectric layer 408 first etch stop film 409 second low dielectric layer 410 second etch stop film 4 11 anti-reflection film 412 photoresist mask 413 via hole; first etching space 4 14a embedding material layer 4 14 b embedding material 415 anti-reflection film 4 16 photoresist pattern 417 trench 4 18 interlayer circuit 4 19 upper circuit layer 501 copper circuit layer 502 substrate 503 first barrier layer 504 first low medium Electrode layer 505 second barrier layer 506 second low dielectric layer -65- (62) photoresist layer photoresist pattern type interlayer underlayer film intermediate layer film upper layer film upper layer photoresist pattern lower layer pattern second low Dielectric layer trench - 66·

Claims (1)

94. 〇3 I25S635 一一Jl, /•r A pick up, patent application scope 92133232 Patent application Chinese patent application scope amendments October 3, 1994, the defender 1 · A lithography underlayer film forming material, A material for providing an underlayer film on the substrate before the die is formed on the semiconductor substrate, and is characterized in that: 3 has at least a specific energy applied and the terminal is detached to generate a sulfonic acid residue. The resin component and solvent of the substituent. 2) - an underlayer film forming material for a germanium two-layer photoresist process, which is formed by forming a lower layer film containing a second layer of light for forming a circuit layer on a substrate with high precision. : A resin component and a solvent containing at least a substituent having a specific energy and a terminal group desorbed from a sulfonic acid residue. 3. The underlayer film forming material for a two-layer photoresist process according to claim 2, wherein the resin component has at least the following general formula (1) (wherein n is an integer of 1 to 1000, a linear or branched alkyl chain having 1 to 10 carbon atoms, an aromatic or alicyclic cyclic alkyl chain, an alkyl ester chain' is specifically The application of energy produces a repeating unit of the substituent of the sulfonic acid residue) 1258635. 4. The underlayer film forming material for a bismuth-containing two-layer photoresist process according to claim 2, wherein the specific energy applied to generate the sulfonic acid residue is light or/and heat. 5. The underlayer film forming material for the second-layer photoresist process according to item 3 of the patent application, wherein the substituent γ of the above general formula (1) is -S03R! or -S〇3_R2+ (wherein R^R2 is Carbon number υο organic basis). 6. The underlayer film forming material for a ruthenium-containing two-layer photoresist process according to claim 5, wherein the organic group 1 is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms or a base group. 7. The underlayer film forming material for a bismuth-containing two-layer photoresist process according to claim 5, wherein the organic group r2 is selected from the group consisting of alkanolamines having a carbon number of 1 to 10, and at least one of the terpene-based fee . 8. The underlayer film forming material for a bismuth-containing two-layer photoresist process according to claim 2, wherein the resin component having at least a specific energy and the terminal group is detached from a substituent which generates a sulfonic acid residue is applied for A resin component of the fourth aspect of the patent, a copolymer or a mixed resin with acrylic acid or methacrylic acid or such derivatives. 9. The underlayer film forming material for a bismuth-containing two-layer photoresist process according to claim 2, wherein the resin component having at least a specific energy and the terminal group is detached from a substituent which generates a sulfonic acid residue is applied for a copolymer or mixed resin of a resin component of the fourth aspect of the patent with acrylic acid or methacrylic acid or such derivatives, as defined in the following general formula (2) -2- 1258635 (wherein n is an integer of 1 to 1000, and R3 is a hydrogen atom, a fluorine atom, a hydroxyl group, a carboxyl group, a hydroxyalkyl group having 1 to 5 carbon atoms, and an alkyloxyalkyl group having 1 to 5 carbon atoms; a copolymer of at least one of a Z-based linear or branched alkyl chain having 1 to 10 carbon atoms, an aromatic or alicyclic cyclic alkyl chain, an alkyl ester chain, or the like A resin component obtained by mixing a resin compound of a repeating unit of the general formula (2). 1 〇. The underlayer film forming material for the bismuth-containing two-layer photoresist process of claim 2, which further contains a crosslinking agent. 1 1. A circuit forming method, comprising: forming on a substrate, using a bismuth-containing two-layer photoresist underlayer film forming material as in claim 2, forming a film forming process under the photoresist underlayer film, A photoresist upper layer film is formed on the underlayer film by using a ruthenium-containing photoresist material, and the photoresist upper layer film is subjected to exposure and development processing to form a photoresist pattern formation process of the specific photoresist pattern type, and the upper layer photoresist pattern is formed. The exposed portion of the underlying film that is not covered is subjected to dry etching to remove the underlying pattern forming process, and the upper layer photoresist pattern and the lower layer pattern are used as masks, and the circuit pattern forming process for etching the substrate to form a specific circuit pattern is performed, and The above-mentioned lower layer pattern and the upper photoresist pattern remaining on the substrate on which the circuit pattern is formed are removed by the photoresist stripping liquid while removing the photoresist pattern. -3- 1258635 1 2, the circuit forming method of claim 11, wherein the photoresist stripping solution used in the forming process of the lower photoresist pattern contains at least a water-soluble amine and a quaternary ammonium hydroxide At least one of them. The circuit forming method of claim 12, wherein the water-soluble amine is at least one selected from the group consisting of an alkanolamine and an alkylamine. 14. An underlayer film forming material for a multilayer photoresist process, comprising a plurality of layers of an underlayer film, an interlayer film, and a photoresist upper film which are formed into a final photoresist pattern on a substrate with high precision on a substrate. The underlayer film forming material of the photoresist process is characterized by comprising a resin component and a solvent having at least a specific energy and a terminal group desorbing a substituent which generates a sulfonic acid residue. 1 . The underlayer film forming material for a multilayer photoresist process according to claim 14 wherein the resin component has at least the following general formula (1); (1) (wherein n is an integer of 1 to 1000, X is a linear or branched alkyl chain having 1 to 10 carbon atoms, an aromatic or alicyclic cyclic alkyl chain, an alkyl ester chain, an anthracene system A repeating unit that produces a substituent of a sulfonic acid residue by the application of a specific energy. 16. The underlayer film -4- 1258635 forming material for a multilayer photoresist process according to claim 14 of the invention, wherein the specific energy system 8 (the heat of TC or more is applied to generate a sulfonic acid residue. 17) The underlayer film forming material for the multilayer photoresist process of the fifteenth aspect of the patent, wherein the substituent Y of the above general formula (1) is -SChRi or -SCh_R2 + (wherein 1 and 1 are an organic group having 1 to 10 carbon atoms) ). 18. The underlayer film forming material for a multilayer photoresist process according to the πth aspect of the invention, wherein the organic group is selected from the group consisting of an alkyl group having a carbon number of 丨 to ... or a hydroxyalkyl group. The underlayer film forming material for a multilayer photoresist process according to claim 17, wherein the organic group R2 is at least one selected from the group consisting of an alkanolamine having a carbon number of 10 and an alkylamine. 20. The underlayer film forming material for a multilayer photoresist process according to claim 14, wherein the resin component having at least a specific energy and the terminal group is detached from a substituent which generates a sulfonic acid residue is as claimed in claim 1 A resin component of item 7 and a copolymer or mixed resin of acrylic acid or methacrylic acid or the like. 21. The underlayer film forming material for a multilayer photoresist process according to claim 14, wherein the resin component having at least a specific energy and the terminal group is desorbed to generate a mineral acid residue is as claimed in the patent application. Copolymer or mixed resin of 树脂7 item of resin component with acrylic acid or methacrylic acid or such derivatives, in the following general formula (•5-2) · 1258635 R3 (2) (wherein n is an integer of 1 to 1000, and R3 is selected from the group consisting of a hydrogen atom, a fluorine atom, a hydroxyl group, a carboxyl group, a hydroxyalkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 5 Repetitive unit copolymerization of at least one of alkyloxyalkyl groups, Z-based linear or branched alkyl chains having 1 to 10 carbon atoms, aromatic or alicyclic cyclic alkyl chains, alkyl ester chains) A resin component obtained by mixing a copolymer or a mixed resin of a resin compound having a repeating unit of the above general formula (2). 22. The underlayer film forming material for a multilayer photoresist process according to claim 14 of the patent application, which further comprises a crosslinking agent. 23. A method of forming a circuit, comprising: forming a material on a substrate using a lower layer film forming material for a multilayer photoresist process as disclosed in claim 14 of the patent application, forming a film formation process under the photoresist underlayer film, Forming an intermediate layer film of the photoresist intermediate layer film on the underlying film, forming a photoresist upper layer film on the intermediate layer film, and applying an exposure and development process to the photoresist upper layer film to form a specific light Blocking pattern upper layer photoresist pattern forming process 5: The exposed portion of the intermediate layer film not covered by the upper photoresist pattern is formed by dry etching to remove the intermediate layer pattern forming process, and the intermediate layer pattern is used as a mask The exposed portion of the underlying film of the uncovered portion of the mask is removed by dry etching to remove the underlying photoresist pattern forming process 1258635. The underlying pattern is used as a mask to etch the interlayer insulating layer on the substrate to form a specific circuit pattern. The circuit pattern forming process and the above-mentioned lower layer pattern remaining on the substrate after forming the circuit pattern are removed by the photoresist stripping liquid to remove the underlying pattern . 24. The circuit forming method according to claim 23, wherein the photoresist stripping liquid used in the forming process of the lower layer pattern contains at least one selected from the group consisting of a water-soluble amine and a quaternary ammonium hydroxide. 25. The circuit forming method according to claim 24, wherein the water-soluble amine is at least one selected from the group consisting of an alkanolamine and an alkylamine. 26. The circuit forming method of claim 23, wherein the tantalum oxide film material for forming the intermediate layer is selected from (A) Si (OR1) a ( OR2 ) b ( 〇R3 ) c ( OR4 d (wherein R1, R2, R3 and R4 are each independently, an alkyl group having 1 to 4 carbon atoms or a phenyl group, a, b, c and d are 0SaS4, 0SbS4, 0Sc$4, 〇SdS4, and satisfy a + b + c + d = an integer of the condition of 4), (B) R5Si ( OR6 ) c ( OR7 ) f ( OR5 ), (wherein R 5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R6, R7 and R8 are each an alkyl group having 1 to 3 carbon atoms or a phenyl 'e,f and g system OS eg 3, 〇$ f S 3, 〇$ g S 3 and satisfying e + f+g = a combination of the conditions of 3) 1258635, and (c) R9R10Si (OR11) h (OR12) (wherein R9 and R1() are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Rii and R12 each are an alkyl group having 1 to 3 carbon atoms or a phenyl group; h and i are 〇sh^2, 〇 A hydrolyzate of at least one compound of a spin-on glass material of S i S 2 and an integer satisfying the condition of h + i = 2. 27. The double damascene structure forming embedding material for forming a first etching space formed by at least a low dielectric layer formed on the substrate and communicating the first etching space and the first uranium engraving space shape and An etching space embedding material of a double damascene structure composed of a second etching space of different sizes, characterized by: A resin component and a solvent containing at least a substituent having a specific energy and a terminal group derived from a sulfonic acid residue. 28. The embedding material for forming a double damascene structure according to claim 27, wherein the resin component has at least the following general formula (1) -8 - 1258635 (wherein η is an integer from 1 to 1000, X is a linear or branched alkyl chain having 1 to 10 carbon atoms, an aromatic or alicyclic cyclic alkyl chain, an alkyl ester chain , γ is a repeating unit that is subjected to the application of a specific energy to produce a substituent of a sulfonic acid residue. 29. The embedding material for forming a double damascene structure according to claim 27, wherein the specific energy applied to generate the sulfonic acid residue is heat of 80 ° C or higher. 30. The embedding material for forming a double damascene structure according to claim 28, wherein the substituent of the above general formula (1) is a SchrR!--SCV R, (wherein Ri and R2 are carbon numbers 1 to 10) Organic base). 3. The embedding material for forming a double damascene structure according to claim 30, wherein the organic group is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group. The embedding material for forming a double damascene structure according to claim 30, wherein the organic group r2 is at least one selected from the group consisting of an alkanolamine having 1 to 1 carbon atoms and an alkylamine. 33. The embedding material for forming a double damascene structure according to claim 27, wherein the resin component having at least a specific energy and the terminal group is separated from a substituent which generates a sulfonic acid residue is as claimed in claim 30 a resin component of the article, a copolymer or a mixed resin with acrylic acid or methacrylic acid or such derivatives. 34. The embedding material for forming a double damascene structure according to claim 27, wherein the above-mentioned resin component having at least a specific energy and the terminal group is separated from a substituent which generates a sulfonic acid residue, -9- 1258635 The resin component of the 30th item of the patent scope and the copolymer or mixed resin of propyl citrate or methyl acrylate or the derivatives are as follows: (wherein n is an integer of 1 to 1000, and R3 is selected from the group consisting of a hydrogen atom, a fluorine atom, a hydroxyl group, a carboxyl group, a hydroxyalkyl group having 1 to 5 carbon atoms, and a valence of 5 to 5 a copolymer of repeating unit copolymerization of at least one of a Z-based linear or branched alkyl chain having 1 to 10 carbon atoms, an aromatic or alicyclic cyclic alkyl chain, and a quaternary acetal chain; A resin component obtained by mixing a resin compound of a repeating unit of the formula (2). 3 5. An embedding material for forming a double damascene structure as claimed in claim 27, which further contains a crosslinking agent. 3 6 · a method for forming a double damascene structure, characterized by: forming an interlayer insulating layer formed by laminating an interlayer insulating layer formed of at least a low dielectric layer on a substrate having a metal layer, in the interlayer insulating layer Forming a photoresist layer on the upper surface, and performing a developing process to form a photoresist pattern, wherein the photoresist pattern is used as a mask to etch the first etching space formed by forming the first etching space in the interlayer insulating layer- 10- 1258635 is coated on the interlayer insulating layer by using an embedding material as disclosed in claim 27, forming an embedding material layer, and filling the embedding material in the embedding process of the first uranium engraving space, Forming a photoresist layer on the embedding material layer, irradiating the pattern light on the photoresist layer, and developing the image with a 2.38 wt% TMAH developing solution to form a photoresist pattern forming process of the photoresist pattern. Etching, using the photoresist pattern as a mask, removing the interlayer insulating layer on the upper portion of the first etching space by a specific pattern to form a second etching space forming process of the second etching space in communication with the first etching space, And an embedding material removing process of removing the embedded material remaining in the second etching space by using a stripping solution. 37. The method for forming a double damascene structure according to claim 36, further comprising: forming an antireflection film forming process of the antireflection film on the embedding material layer on the interlayer insulating layer after the embedding process; After the photoresist pattern forming process, the resistive pattern is used as a mask to process the exposed portion of the anti-reflection film by dry etching. 3. The method of forming a double damascene structure according to claim 36, wherein the stripping liquid for the above-mentioned embedding material removing process contains at least one selected from the group consisting of water-soluble amines and quaternary ammonium hydroxides. 39. The method of forming a dual damascene structure according to claim 38, wherein the water-soluble amine is selected from the group consisting of alkanolamines and at least one of alkylamines. -11 -